The cobalt core exhibits an approximately square-pyramidal geometry with partially reduced thienyl radical monoanionic ligands. The supramolecular network is consolidated by hydrogen-bonding interactions primarily with nitrogen, sulfur and chlorine atoms, as well as parallel displaced π-stacking of the aryl rings. The UV–vis, IR, and CV data are also consistent with monoanionic dithiolene ligands and an overall CoII oxidation state.The title compound, bis(1,2-diphenyl-2-sulfanylideneethanethiolato-κ The cobalt dithiolene core is approximately planar, with angles of 89.73 (2)° for S1—Co1—S2, 88.93 (2)° for S1—Co1—S3, 88.41 (2)° for S2—Co1—S4, and 89.90 (2)° for S3—Co1—S4. The sum of the angles is 356.97 (4)°, consistent with only a slight distortion from planarity. The PTA ligand occupies a 5th coordination site with angles of 101.94 (2)° for P1—Co1—S1, 98.12 (2)° for P1—Co1—S2, 90.97 (2)° for P1—Co1—S3, and 97.22 (2)° for P1–Co1—S4. Therefore, the overall geometry of [Co(pdt)2(PTA)] is approximately square pyramidal.[Co(pdt)p-anisyl-substituted analogues with PMe3 and PPh3 2(PTA)] is attributed to the small cone angle of 103°  Å for Co1—S1, 2.1669 (6) Å for Co1—S2, 2.1685 (5) Å for Co1—S3, and 2.1487 (5) Å for Co1—S4. These are mostly within the range of Co—S distances of 2.1659 (9)–2.1765 (9) Å reported for the p-anisyl-substituted analogues with PMe3 and PPh3, respectively  Å for S1—C7, 1.719 (2) Å for S2—C8, 1.729 (2) Å for S3—C21, and 1.731 (2) Å for S4—C22. These are mostly within the range of S—C distances of 1.721 (2)–1.726 (3) and 1.730 (3)–1.742 (3) Å reported for the 2(PTA)] and one molecule of 1,2-dicholorethane are present in the unit cell, as depicted in Fig. 3ii distance of 2.78 Å Å Figs. 3, #2 ▸ anb axis, parallel displaced π-stacking of the aryl rings is revealed  Å apart °, while the sum of the angles is 356.97 (6)° for the PMe3 complex. Similarly, the phosphine in PPh3 is axially distorted because of the steric bulk of the phenyl groups, resulting in two more obtuse bond angles for S2—Co1—P1 and S3—Co1—P1 of 101.31 (3) and 106.6 (3)°, respectively. The other bond angles of 92.81 (3)° for S1—Co1–P1 and 97.13 (3)° for S4—Co1—P1 are within the range of S—Co1—P1 angles of 91.19 (3) to 99.65 (3)° observed for the PMe3 complex.A survey of the Cambridge Structural Database ] was conducted in dichloromethane  transition, based on comparison with the related iron complex with PPh3  complex. The IR signal for [Co(pdt)2(PTA)] at 1157.61 cm−1 is characteristic of monoanionic dithiolenes with a π-radical when coordinated to metals, and is attributed to ν(C=S·) ne Fig. 5 and reve2(PTA)] was collected in a solution of dichoromethane with a platinum working electrode  of [Co(pdt)de Fig. 6 and a glde Fig. 6. Both CV2(pdt)4]  and PTA  under an N2 atmosphere. To this mixture of solids, 20 mL of CH2Cl2 were added and stirred for 4 h at room temperature. The solvent was removed under reduced pressure and the resulting dark-orange solid was washed with 3 × 5 mL of Et2O and dried under vacuum. The product was stable under reduced pressure and at room temperature. Yield: 92% . Crystals suitable for X-ray diffraction were grown by the vapor diffusion method with diffusion of pentane over a 1,2-dichloroethane solution of the compound. UV–Vis spectra were obtained at ambient temperature with a Varian Cary 50 diode array spectrometer, while IR spectra were taken neat with an ALPHA FTIR instrument. Electrochemical measurements were performed with a CHI600E electroanalyzer workstation using an Ag/AgCl reference electrode, a platinum disk working electrode, a platinum wire auxiliary electrode, and [nBu4N][PF6] as the supporting electrolyte in CH2Cl2. Under these conditions, the [Cp2Fe]+/ Cp2Fe couple consistently occurred at +440 mV. UV–vis in CH2Cl2: : 301 nm (17881), 877 nm (6428). IR spectroscopy (cm−1): 3366.53 (w), 3054.34 (w), 2928.02 (w), 2869.68 (w), 1592.50 (w), 1440.63 (m), 1415.07 (s), 1275.25 (m), 1240.54 (w), 1157.61 (m), 1091.56 (s), 1012.49 (m), 969.10 (s), 940.65 (vs), 739.50 (s), 693.31 (s).A 50 mL Schlenk flask containing a stir bar was charged with [Co2, respectively, and refined using a riding model with Uiso(H) = 1.2 Ueq(C) for CH and CH2.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020005447/zl2776sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020005447/zl2776Isup2.hklStructure factors: contains datablock(s) I. DOI: 1986931CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-019-42476-4, published online 11 April 2019Correction to: The original version of this Article contained errors.In the Abstract,“The comparison of the mean load to failure of all 3 groups  did not reveal a significant difference.”now reads:“The comparison of the mean load to failure of all 3 groups  did not reveal a significant difference.”In Table 1,2”.“Stiffness in N/mmnow reads:“Stiffness in N/mm”2”, row r7,Furthermore, in column “Strength in N/mm“-27.1”now reads:“27.1”Additionally Table 1 contained errors in the values in columns Stiffness in N/mm, Strength in N/mm², Cross sectional area in mm². The original Table As a result of this, in the Results section,2 . There was no significant difference between mean stiffness  and strength . A detailed overview is presented in Table “The mean cross sectional area of ROI (fracture region) was 1.81 mmnow reads:2 .There was no significant difference between mean stiffness  and strength . A detailed overview is presented in Table “The mean cross sectional area of ROI (fracture region) was 1.72 mmAnd,“No significant difference in the load to failure values between the three groups was found (p  =  0.113). The mean load to failure in group 1 was 28.7  ±  6.1 N  compared to 23.8  ±  3.8 N  in group 2. The mean load to failure in group 3 was 23.7  ±  5.7 N .”now reads:“No significant difference in the load to failure values between the three groups was found (p = 0.113). The mean load to failure in group 1 was 28.7 ± 6.4 N  compared to 23.7 ± 6.0 N  in group 2. The mean load to failure in group 3 was 24.0 ± 3.9 N .”These errors have now been corrected in the PDF and HTML versions of the Article.


Hydrogen bonding of the anions is restricted to F-atom acceptors only, with particularly strong N–H⋯F interactions [N⋯F = 2.5072 (15) Å] established by axial and cis-positioned equatorial F atoms.In the structure of the title salt, second-order Jahn–Teller distortion of the coordination octahedra around V ions is reflected by coexistence of short V—O bonds and  7H12N6)[VOF5], second-order Jahn–Teller distortion of the coordination octahedra around V ions is reflected by coexistence of short V—O bonds [1.5767 (12) Å] and trans-positioned long V—F bonds [2.0981 (9) Å], with four equatorial V—F distances being intermediate in magnitude [1.7977 (9)–1.8913 (9) Å]. Hydrogen bonding of the anions is restricted to F-atom acceptors only, with particularly strong N–H⋯F interactions [N⋯F = 2.5072 (15) Å] established by axial and cis-positioned equatorial F atoms. Hirshfeld surface analysis indicates that the most important interactions are overwhelmingly H⋯F/F⋯H, accounting for 74.4 and 36.8% of the contacts for the individual anions and cations, respectively. Weak CH⋯F and CH⋯N bonds are essential for generation of three-dimensional structure.In the structure of the title salt, (C MvOF5]2− series  of ions [VOF5] [VOF5] ·[VOF5]2−, which gives insight into the hydrogen-bonding behaviour of [VOF5]2− anions when combined with the bitopic nitrogen-rich 4,4′-bis dication. This cation provides different kinds of hydrogen-bond donor sites complemented by triazole-N acceptors, which are relevant to many types of coordination and hydrogen-bonded systems  Å], which define the local polar axis of the anion. Four equatorial V—F bonds 2− anions in the salts with (H2bipy)2+ 2+ cations  = 103.46 (12) and 104.11 (12)° ° and N3—C5—C6—C7 of −63.73 (17)°. A diversity of metal complexes suggest nearlys equal occurrence of trans–gauche and all-trans sequences for the present moiety  Å .Primary strong N—H⋯F bonding links the ionic counterparts into chains, which aggregate forming layers parallel to the ks Fig. 2. The firThe packing of the layers extends the structure in the third dimension. For every next layer of the succession, the direction of the primary N—H⋯F bonded chains is inclined by 56.8° to the direction of chains from the preceding layer Fig. 3. Links bet al., 2004CrystalExplorer17  to 1.3445 (blue) a.u. indicates a number of red spots related to hydrogen-bond contacts. Particularly prominent spots are associated with the strongest N—H⋯F bonds. However, even the C—H⋯F interaction with the weakest of the present donors  is reflected by a red spot on the surface . In addition to this very sharp spike, the plot clearly reveals the more subtle feature of anion⋯π bonding, which appears as a short spike at 2.7 Å , 0.84 ml of 7% aqueous HF solution (3.0 mmol) and 2 ml of water were placed in a Teflon vessel and heated in a steel bomb at 413 K for 24 h. Cooling to room temperature over a period of 48 h afforded colourless crystals of the title salt, in a yield of 27 mg (40%). Analysis (%) calculated for C7H12F5N6OV: C 24.57, H 3.54, N 24.57; found: C 24.38, H 3.49, N 24.70.The bitriazole was prepared in a yield of 33% by the acid-catalysed condensation of 1,3-diaminopropane and 2) = 0.98 Å; Uiso(H) = 1.2Ueq(CH) and 1.5Ueq(NH).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S205698902000585X/hb7908sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698902000585X/hb7908Isup2.hklStructure factors: contains datablock(s) I. DOI: 1999654CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Of these compounds, 10 and 12 form 1D or 2D coordination polymers in the solid state. (Spectro)Electrochemical studies confirmed reversible Fc/Fc+ redox events between −130 and 160 mV. 1,6‐ and 2,7‐Substitution in 5 a (E°′=−130 mV) and 7 a (E°′=50 mV) influences the redox potentials, whereas the ones of 5 b and 7 b (E°′=20 mV) are independent. Compounds 5 b, 7 b, 10, and 12 show single Fc oxidation processes with redox splittings between 70 and 100 mV. UV/Vis/NIR spectroelectrochemistry confirmed a weak electron transfer between FeII/FeIII in mixed‐valent [5 b]+ and [12]+. DFT calculations showed that 5 bnon‐covalently interacts with the single‐walled carbon nanotube (SWCNT) sidewalls as proven by, for example, disentangling experiments. In addition, CV studies of the as‐obtained dispersions confirmed exohedral attachment of 5 b at the SWCNTs.The synthesis of 1‐Fc‐ (η5‐C5H5)) is discussed. Two of these compounds form 1D or 2D coordination polymers in the solid state. (Spectro)electrochemical studies confirmed reversible Fc/Fc+ redox events between −130 and 160 mV. With the example of 2,5‐Fc2‐cC4H2E (Fc=Fe(η5‐C5H4)(η5‐C5H5); E=O, S, NR), it could be shown that similar geometries and hence comparable electrostatic interactions enable a correlation between electrochemical and spectroscopic properties.Redox‐active ferrocenyl‐functionalized five‐non‐covalent interactions, for example, π–π stacking.Furthermore, aromatics are suitable to modify carbon nanotubes (CNTs) by + (NADH=dihydronicotinamide adenine dinucleotide).Ferrocene‐functionalized CNT nanohybrids have attracted much attention in the fields of (bio)analytical electrochemistry,N‐(pyren‐1‐ylmethyl)propanamide to SWCNTs and tested as glucose sensor electrode materials.6)2.II/RuIII redox potential is stable over 200 cycles. Another hybrid material is CNT/cobalt bis‐pentyl]butyramide).Non‐covalently functionalized CNTs bearing a ferrocenyl substituent were recently obtained through π‐stacking of 3‐ferrocenyl‐Lately, we became interested in attaching redox‐active Fc‐functionalized polyaromatic hydrocarbons to SWCNTs as a way to achieve debundeling as well as to influence the electronic properties of the thus‐modified carbon nanotubes and to use them as field‐effect sensors.2‐, and 2,7‐Fc2‐pyrenes, 3,6‐Fc2‐9,10‐phenanthrenedione, and 3,6‐Fc2‐9,10‐dimethoxyphenanthrene compounds is discussed. Their (spectro)electrochemical properties and their molecular structures in the solid state are reported. DFT calculations for 1,6‐Fc2‐pyrene and semiconducting and metallic SWCNTs are provided, as well as the use of 1,6‐Fc2‐pyrene to disentangle SWCNTs. The electrochemical properties of the as‐obtained dispersions are presented.Hence, within this study, the synthesis and characterization of a series of 1‐Fc‐, 1,6‐Fc3, 5 a,b, 7 a, 10) or Negishi  C−C cross‐coupling reactions were applied (η5‐C5H5)) was treated with the respective 1‐Br‐ (2), 1,6‐Br2‐ (4), 2,7‐Br2‐pyrene (6), or 3,6‐Br2‐9,10‐phenanthrenedione (9) in the presence of [PdCl2(dppf)] ferrocene) as the catalyst in the molar ratio of 1:1 or 2:1 in boiling toluene. After appropriate work‐up, compounds 3, 5 a,b, 7 a, and 10 could be isolated as orange  or green (10) solids in a yield of 3–65 % . For comparison, compound 9‐ferrocenylphenanthren was synthesized according to the Suzuki C−C cross‐coupling protocol used within the synthesis of 3, 5 a,b, 7 a, and 10 .Ferrocene boronic acid FcB(OH)1 with 1,6‐Br2‐C16H8 (4) in the molar ratio of 2:1, a mixture of the respective mono‐ and diferrocenyl‐functionalized pyrenes 5 a,b was formed .In the transmetalation reaction of 1 with 2,7‐Br2‐C16H8 (6) in a 2:1 ratio in boiling toluene solely gave the monoferrocenyl‐substituted species 2‐Br‐7‐Fc‐pyrene (7 a), which was obtained as an orange solid in a yield of 32 % after column chromatography 6 in the presence of 1.0 mol % [PdCl2(dppf)] as the catalyst in boiling tetrahydrofuran produced 7 b, however, in a yield as low as 2 % . In this reaction, other than 7 b, ferrocene was formed as the main product. Compound 7 b is a very poorly soluble species in common polar organic solvents. Once 7 b was isolated in its solid form, it was almost impossible to redissolve it and hence spectroscopic and electrochemical experimental data on this organometallic compound are limited.However, diferrocenyl pyrene 10 and 12 were synthesized by either the Suzuki–Miyaura (10) or the Negishi (12) reaction starting from 3,6‐dibromophenanthrene‐9,10‐dione 9  in toluene in the presence of catalytic amounts of [PdCl2(dppf)] led to the formation of green 3,6‐diferrocenylphenanthrene‐9,10‐dione (10) in a yield of 28 %. However, the synthetic methodology described by Phulwale et al. for the reduction of the ketone functionalities in 10 did not lead to the formation of the respective 3,6‐diferrocenyl‐9,10‐dimethoxyphenanthrene compound 12.9 was performed prior to the C−C cross‐coupling reaction. Thus, compound 11 could be isolated in virtual quantitative yield. Upon treatment of 11 with two equivalents of FcZnCl (8) in tetrahydrofuran as solvent for 24 h in the presence of [PdCl2(dppf)] gave orange 12 in an overall yield of 13 % .Compounds 5 a,b, 7 a,b, 10, and 12 was confirmed by elemental analysis, IR, 1H and 13C{1H} NMR spectroscopy, and high‐resolution ESI‐TOF mass‐spectrometry , whereas the physical and analytical data  of 3 are documented in reference 7 b).The identity of 1H, 13C{1H} NMR) data of 3, 5 a,b, 7 a,b, 10, and 12 are consistent with their formulations as mono‐ or diferrocenyl‐functionalized pyrene, 9,10‐phenanthrenedione, and 9,10‐dimethoxyphenanthrene compounds, showing the characteristic coupling patterns of the appropriate isomers .7 b no reliable 13C{1H} NMR data could be obtained, owing to its low solubility in common polar organic solvents (see above).The spectroscopic , I2/a (5 a), P21/n (5 b), or P21/c  and in the orthorhombic space groups Pnn2 (12) and P212121 (9‐ferrocenylphenanthrene) with one  or two (10) independent molecules in the asymmetric unit. Intermolecular π–π interactions were investigated between the aromatic entities and the ferrocenyl cyclopentadienyl units .The compounds crystallize in the monoclinic space groups ipso‐carbon atoms and the aromatic units is similar for all investigated compounds (from 1.476(3) Å (7 a) to 1.554(8) Å (10)) and agree well with literature values.The distance between the ferrocenyl cyclopentadienyl  to 1.554 Å (10)) In Tables SI3 and SI4 (in the Supporting Information), the bond lengths of the different aromatic cores are summarized. The substitution pattern does not affect the position of the single and double bonds in the aromatic moieties. This observation is in good agreement with values published for other substituted pyrenyl and phenanthrenyl derivatives.3, 5 a,b, 7 a,b, 12, and 9‐ferrocenylphenanthrene. Compounds containing hydrogen atoms in position 8 with regard to the Fc group  possess increased values of 31.5(5)° (5 b) to 40.05(10)° (5 a), owing to a steric interaction with the α‐H atoms of the ferrocenyls. In contrast, the geometric properties of the 2‐ or 3‐substitution pattern  allow for more planar intersections between 0.1(3)° (10) and 22.1(9)° (12). Hence, these compounds should be preferred to achieve a high degree of electron transfer interaction between the π‐system of the ferrocenyls and the aromatic cores.3, 5 a,b, and 9‐ferrocenylphenanthrene argue for a weak interaction. In addition, the rms distortions (root mean square deviations) of the condensed aromatic units were calculated and are summarized in Table SI5 (in the Supporting Information), where 5 a (0.0497) and 12 (0.0680) showed exceptional high values.The rotation of the ferrocenyls out of the aromatic co‐planarity was examined for 5 b, 7 b, 10, and 12 exhibit an anti‐positioning of the Fc groups towards each other with regard to the aromatic planes.10) to 12.7288(8) Å (7 b). Thereby, the Fe⋅⋅⋅Fe distances in 10 (9.0374(13) Å Fe1–Fe2; 9.0390(13) Å, Fe3–Fe4) and 12 (10.123(6) Å) point towards a better electronic coupling between the ferrocenyl groups than in 5 b (11.477(2) Å) and 7 b (12.7288(8) Å).The diferrocenyl‐substituted compounds 3, 5 a,b, 7 a,b, 10, 12, and 9‐ferrocenylphenanthrene as π‐surfactants on CNTs, the interaction through intermolecular π/C−H⋅⋅⋅π bonding was investigated for the aromatic and ferrocenyl units . Except for 7 b, all compounds show intermolecular π–π interactions , of which 3, 5 b, and 9‐ferrocenylphenanthrene show T‐shaped π‐interactions between C5H5/C5H4 units and the aromatic moieties with distances of 4.5276(14) (3)–4.994(6) Å (5 b). The solid‐state structures of 5 a and 7 a show T‐shaped and parallel displaced π‐interactions with distances between 4.6081(17) (5 a) and 4.6925(14) Å (7 a) and angles from 84.68(15) (5 a) to 89.24(14)° (7 a). The parallel displaced π‐interactions between the pyrene cores of 5 a and 7 a show distances of approximately 3.6 Å, forming dimers .With regard to the utilization of 10 and 12, the parallel displaced π‐interactions between the arenes led to the formation of 1D (12) and 2D coordination polymers (10) along the a‐ (10) or b‐axis (12), resulting in the formation of columns . The columnar structure of 12 is based on the parallel displaced π‐interactions involving C11–C16 of the phenanthrene with centroid–centroid distances of 5.165(12) Å, exceeding the criterion for π‐stacking (3.3–3.8 Å).In case of 10 builds a 2D coordination polymer, whereby both molecules of the asymmetric unit are responsible for the columnar structure. Parallel displaced π‐interactions between the ferrocenyl's cyclopentadienyls interconnect the columns. The arrangement along the a‐axis is based on the interactions between the arenes of the phenanthrene backbone with distances ranging from 3.589(3) to 4.549(3) Å. Furthermore, this stacking is supported by π‐interactions involving the Fc‐C5H4 units and the aromatic moieties with distances ranging from 3.466(3) to 4.800(3) Å .Compound ṽmax) of compound 10 were measured in a set of 23 common organic solvents of different polarities and hydrogen‐bonding abilities =658 nm =553 nm). This shift corresponds to a positive solvatochromism with a solvatochromic range of Δṽmax (10)=2880 cm−1.Compound The interactions of solvatochromic dyes with pure solvents or solvent mixtures arise from a combination of many effects.α, β, and π*. In addition, ṽmax,0 corresponds to a standard process, referenced to a nonpolar medium. The parameters a, b, and s represent solvent‐independent correlation coefficients, which reflect the relative effect of each of the three parameter α, β, and π*.According to Equation (1), the effect of hydrogen‐bonding donor capacity (HBD),α, β, and π* used for the multiple linear regression analysis are given in Table SI6 (in the Supporting Information).10, which is qualitatively the best according to the solvent scales of Kamlet–Taft, is given in Table The solvent parameters r is greater than 0.90 for the LSE relationship, indicating a high validity of the multiparameter equation, allowing significant conclusions to be drawn. Compound 10 shows a positive solvatochromism with increasing acidity and dipolarity/polarizability of the solvents.The correlation coefficient s indicates that the electronically excited state of 10 becomes solvated stronger and is consequently stabilized with increasing solvent dipolarity/polarizability. Owing to the strength of the higher dipole moment, the energy of the electronically excited state decreases more than the energy of the ground state. This is in good agreement with a bathochromic shift of the UV/Vis absorption maxima with increased polarity of the solvent.The negative sign of a for 10 indicates that there is a bathochromic shift of λmax with increasing hydrogen‐bond donor capacity of the solvent (positive solvatochromism). Owing to the solvation of the carbonyl oxygen atom by HBD solvents the push–pull character becomes enhanced. This effect is on the same order of magnitude as the influence of the dipolarity/polarizability. The hydrogen‐bond acceptor capacity of the solvents, on the other hand, has no influence on the solvatochromic behavior of 10 (b=0).The negative sign of parameter ṽmax) of 1820–2460 cm−1 in contrast to 10 with 2880 cm−1, which indicates a stronger solvatochromic behavior.A similar behavior was observed for ferrocenyl‐substituted maleimides.3, 5 a,b, 7 a,b, 10, and 12 were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), and spectroelectrochemistry (in situ UV/Vis/NIR). As supporting electrolyte, an anhydrous dichloromethane solution containing 0.1 mol L−1 of [NnBu4][B(C6F5)4] was used.6]− or [Cl]−, [B(C6F5)4]− stabilizes highly charged species in solution and minimizes ion pairing effects.+ redox couple.−1 are summarized in Table The redox properties of compounds 3  as well as 5 b, 7 b, 10, and 12  show one  or two  reversible redox processes. The aromatic cores are characterized by a reversible (5 a) or irreversible redox event  between 950 and 1250 mV, however, for 7 b, 10, and 9‐ferrocenylphenanthrene no oxidation of the aromatic core occurred under the applied measurement conditions.The Fc groups of 9‐ferrocenylphenanthrene and 5 a, 7 a), the substitution pattern  and the nature of the aromatic core . Comparison with 3 shows that the bromo substituent has a strong impact on the electron density at Fc, shifting the potential by 160 mV anodically. The Fc‐based redox process of 7 a is further shifted to 50 mV (vs. FcH/FcH+) compared with 3. Positions 2 and 7 are electron‐poor5 a. This observation is in contrast to the investigations of Fc‐substituted naphthalenes, where the influence of the substitution pattern is stronger than the impact of electron‐withdrawing entities like bromine.3 and 9‐ferrocenylphenanthrene, respectively. Dhokale et al. reported that 1‐ferrocenylpyrene and 1‐ferrocenylethynylpyrene show Fc‐based oxidations at 50 and 70 mV when using [NnBu4][PF6] as the electrolyte versus a saturated calomel electrode (SCE).nBu4][B(C6F5)4] as a weakly coordinating electrolyte.Within the series of monoferrocenyl‐substituted pyrenes, compound 5 b and 7 b show a single redox event for both ferrocenyl groups at 20 mV  and 100 mV pyrene by using [NnBu4][PF6] as the electrolyte.tert‐butyl‐9 H‐carbazol‐9‐yl)pyrene) to 100 mV pyrene), which is in good agreement with the results observed for 5 b and 7 b.5‐C5Me5)(dppe)RuC≡C)2‐pyrene, which showed a value of 120 mV.Diferrocenyl pyrenes es Table  point to10 and 12 were synthesized to investigate the influence of electron‐withdrawing and ‐donating groups on the redox potential of the ferrocenyl oxidation. The methoxy‐functionalized compound 12 shows a redox process at 30 mV (vs. FcH/FcH+). In contrast to that, the electron‐withdrawing keto groups in positions 9 and 10 of 10 decrease the electron density of the Fc entities and therefore shift the respective potential by 130 mV anodically. The redox separation of 10 and 12 is lower than for the appropriate diferrocenyl‐substituted pyrenes 5 b and 7 b. By deconvolution of the SW voltammograms, redox splittings of 70 (10) and 80 mV (12) were found, pointing to a weak metal–metal interaction based on either electrostatic interactions or electron transfer  measurements were performed. Compound 7 b could not be investigated by this method, owing to its low solubility. Furthermore, the UV/Vis/NIR investigations of 10 revealed no intervalence charge transfer (IVCT) absorption but a MLCT  transition, which is in good agreement with the postulated resonance structures (Scheme SI2 in the Supporting Information).For the purpose of classification, the electron transfer between the Fc/Fc5 b and 12) or propylene carbonate solutions (12) containing 5 b or 12 (2.0 mmol L−1) and [NnBu4][B(C6F5)4] (0.1 mol L−1) as supporting electrolyte in an OTTLE  cell.5 b and 12. During the measurements, oxidation of the neutral compounds to mixed‐valent [5 b]+ and [12]+ and finally to the fully oxidized species [5 b]2+ and [12]2+ was observed  gave mixed‐valent species [5 b]+ and [12]+ and hence a broad absorption within this area (800–3000 nm) was observed. A further increase in the potential resulted in a decrease of this band, which is characteristic for intervalence charge transfer excitations  and therefore the small comproportionation constants  lead, in the best case, to a mixture consisting of an equilibrium of 73 % mixed‐valent monocationic [12]+ as well as 13.5 % neutral 12 and di‐cationic species [12]2+ each. As the composition of this equilibrium is not determinable by using an OTTLE cell, the extinction values are associated with considerable uncertainties.For neutral 5 b and 12. The NIR data of the IVCT absorptions are summarized in Table The observed spectra were deconvoluted into three Gaussian‐shaped bands, which represent a LF (ligand field),5 b and 12 showed no absorption in the NIR region, whereas mixed‐valent [5 b]+ and [12]+ have weak and broad absorptions between 750 and 2000 nm. The IVCT bands of Fc‐substituted aromatics 5 b and 12 exhibit different characteristics . The highest intensity of 510 L mol−1 cm−1 was found for 575 mV (vs. Ag/Ag+). From Figure SI20 (in the Supporting Information), it can be seen that in the series of increasing potential the IVCT absorption increases until its maximum at 575 mV, followed by a decrease of intensity upon further oxidation to [5 b]2+ and an increase of LMCT. The determined values of the IVCT absorption of 5 b are in good agreement with 2,7‐bispyreneNeutral cs Table . For 5 b12 leads to a more intense and narrow IVCT absorption  than in Fc2‐substituted pyrene 5 b and is further shifted hypsochromically compared with the metal–metal interaction band of 5 b. This statement is based on the higher electron density of the dimethoxy‐substituted phenanthrene moiety, which was observed in the CV measurements (Table 12 is oxidized more easily (1110 mV vs. FcH/FcH+) than the pyrenyl connectivity of 5 b .The smaller π‐conjugated bridge present in μ=4.9 D) was further chosen as an additional solvent for the spectroelectrochemical measurements of 12. Analogous investigations on 5 b failed in the UV/Vis/NIR setup, owing to its insufficient solubility in propylene carbonate. In the case of [12]+, the IVCT transition could be detected at approximately 11 000 cm−1 by using the solvent with higher polarity, revealing a solvatochromic shift (Δνmax) of 1000 cm−1 (Table νmax in comparison for very strongly coupled systems (Δνmax≈100 cm−1)Within these species, the IVCT bands typically show strong solvatochromism.3, 5 a,b, 7 a, and 12 were investigated, except for 10, which showed a MLCT . The UV/Vis/NIR spectra are depicted in Figures SI17–SI19, SI21, SI22, SI24, and SI25 in the Supporting Information). The respective LMCT data of [3]+, [5 a]+, [5 b]2+, [7 a]+, and [12]2+ are summarized in Table To gain a deeper insight into the communication between the aromatic core and the ferrocenyl ligands, the ligand‐to‐metal charge transfer properties of E°′, the transition energy νmax is increased. The only exception is 1‐ferrocenylpyrene 3, which shows an anodic shift of its redox event and its transition at 8150 cm−1. This might be based on the fact that the plane intersection of 3 in the solid state exhibits a rms value of 0.0348, which indicates a bent aromatic core. Further, the carbon atom C11 shows the highest displacement with 0.0685(17) Å, confirming a weak interaction between the Fc and the arene moieties (Table SI5 in the Supporting Information). Equivalent correlations have been reported for charge transfer complexes, for example, ferrocenyl naphthalenes,5 a with 7 a, it is clear that a better communication between the Fc and the pyrene building blocks is given by the substitution in positions 1 and 6 than in 2 and 7, owing to higher intensity of the transition for 5 a.The energy of the LMCT absorptions is related to the redox potentials of the Fc entities, displaying that with an increase of th 0.0685 Å, confi5 b for disentangeling and modification studies of the SWCNTs surface. Hence, DFT calculations were additionally carried out to support the respective pyrene–SWCNT interactions.Based on the spectroelectrochemical properties  and that the pyrene connectivity is favored to non‐covalently bind to CNTs,5 b and SWCNTs. Here, we have considered both semiconducting ‐SWCNT and metallic ‐SWCNT as representative models of SWCNTs. Figure 5 b on ‐SWCNT. It was found that the pyrene group of 5 b tends to orient parallel to the CNT surface owing to optimized π–π interactions. The computed pyrene–CNT equilibrium distance and adsorption energy are 3.2 Å and −1.26 eV by using the PBE (Perdew–Burke–Ernzerhof) functional with empirical dispersion corrections (PBE‐D). In contrast, the plain DFT‐PBE calculations predict a much larger pyrene–CNT equilibrium distance (4.1 Å) and a negligible adsorption energy (−0.1 eV). These data indicate that the van der Waals forces are the dominant interactions between 5 b and SWCNTs. This conclusion was also observed for the adsorption of 5 b on a ‐SWCNT surface, suggesting that the diameter and chirality of CNTs have only a small influence on the adsorption mechanism. Additionally, Mulliken population analysis was employed to study the charge transfer in the ground state. The calculation results reveal that only a few electrons (about 0.1 e) are transferred from 5 b to the CNT, which further confirms their π–π interactions.Density functional theory (DFT) calculations were performed to provide mechanistic insights into the interactions between 5 b to interact with SWCNTs in a non‐covalent fashion in solution, debundeling experiments were performed with two commercially available materials: (i) chirality‐enriched ‐SWCNTs as powder  and (ii) NanoIntegris IsoSol S‐100® SWCNT in dispersion. ‐SWCNTs are, owing to their low purity, not suitable for electronic components but are an appropriate model system for the disentangling. However, the NanoIntegris IsoSol S‐100® SWCNT dispersion, consisting of up to 99.9 % semiconducting material, has proven to be an appropriate material for the scalable fabrication of CNT transistors and sensorsTo investigate the ability of 5 b was used for disentangling experiments with the NanoIntegris IsoSol S‐100® SWCNT dispersion and the results thereof are summarized in Figure 5 b are presented in Figure SI26 (in the Supporting Information).As indicated above, compound 5 b by using a vacuum filtration procedure aryl‐based polymer)Gen1 solid, both the S22 and S33 transitions of the SWCNT mixture as well as the PFH‐R transition remain unchanged from a spectral point of view, the relative composition of the absorption spectrum allows us to conclude a first successful depletion step for the reference solid through the vacuum filtration procedure. For the Gen2 solid, the spectrum clearly mimics the SWCNT signature from the Gen0 and Gen1 spectra as well as the particular PFH‐R transition (spectrum PFH‐R (toluene) mathematically deconvoluted from the spill liquid and the Gen0 spectrum). Additionally, the spectrum for the Gen2 solid shows a transition at 352 nm, which can be identified as an absorption feature of 5 b (measured spectrum 5 b (toluene)), which unambiguously indicates that 5 b is present in the redispersed SWCNT solid after the vacuum filtration procedure.In spectrum 0 Figure , the S225 b was further confirmed by electrochemical measurements. The redox properties of the dispersion Gen2 ({5 b}{PFH‐R}@SWCNT) were investigated by cyclic voltammetry by using Gen2‐modified graphene paper−1 KCl. The voltammetry measurements were performed at 25 °C. All potentials are referenced to the SCE using K3[Fe(CN)6] as the internal standard.The functionalization of SWCNTs with Gen2 show a ferrocenyl‐based redox process at 380 mV .The CVs of Ep value of the respective redox processes are characteristic.−1; Table i≈vr0.62; vr=sweep rate), which is far from a linear relationship, but also does not reflect the i≈√vr of a fully dissolved redox system. The redox processes of dispersion Gen2 show ΔEp values between 40 and 55 mV . This emphasizes that 5 b is exohedrally attached to the SWCNTs. In Gen2, where 5 b is π‐bonded to SWCNTs, but not immobilized at the electrode surface, the above criteria for surface‐confined redox couples are unfulfilled, whereas simultaneously the electrochemical system Gen2 does not behave accordingly to homogeneously dissolved redox‐active molecules.To exclude that the redox process of + event is quite stable after polymerization, as the peak current decreases only slightly after five cycles .To investigate the influence of the pyrene core towards the ferrocenyl‐based redox process, the potential area was extended to 900 mV Figure . An irre3), 1‐Br‐6‐Fc‐ (5 a), 2‐Br‐7‐Fc‐ (7 a), 1,6‐Fc2‐pyrene (5 b), and 3,6‐Fc2‐9,10‐phenanthrenedione (10) were synthesized by reacting ferrocene boronic acid (1) with the respective bromo‐functionalized aromatics by applying the Pd‐catalyzed Suzuki C−C cross‐coupling protocol. The Negishi C−C cross‐coupling methodology allowed the formation of 2,7‐Fc2‐pyrene (7 b) and 3,6‐Fc2‐9,10‐dimethoxyphenanthrene (12).Compounds 1‐Fc‐  to 22.1(9)°). Parallel displaced π‐interactions were found for 10 and 12, and 10 and 12 exhibit a columnar stacking between the aromatic building blocks, leading to the formation of 1D (12) or 2D coordination polymers (10) along the a‐ (10) or b‐axis (12).The molecular structures of 3, 5 a,b, 7 a,b, 10, and 12, and 9‐ferrocenylphenanthrene for comparison, revealed a strong impact on the redox processes when bearing electron‐withdrawing or ‐donating functionalities such as Br or OMe units. Within the series 3, 5 a, and 7 a, it could be shown that Br in position 1 influences the redox behavior most by shifting the potential cathodically from 50 mV in 7 a to −130 mV in 5 a (vs. FcH/FcH+). The Fc group in position 1 in 3 (30 mV vs. FcH/FcH+) is more easily to oxidize than the Fc in position 2 in 7 a (E°′=50 mV). However, the 1,6‐ and 2,7‐substitution patterns of pyrenes 5 b and 7 b have no significant influence on the redox potentials and the redox splitting as was reported for Fc2‐naphthalenes,tert‐butyl‐9 H‐carbazol‐9‐yl)‐, and 2,7‐((η5‐C5Me5)(dppe)RuC≡C)2‐pyrenes.+ redox potential of 10 and 12 differ as expected for electron‐withdrawing (C(=O)) or ‐donating (MeO) groups in positions 9 and 10 of the phenanthrene core. The redox splitting in the latter species is smaller than in pyrenes 5 b and 7 b, which is based on the closer proximity of the Fc ligands and the more electron‐poor π‐conjugated bridge in 10 and 12.Electrochemical studies of the Fc‐substituted aromatics 5 b, 10, and 12, in situ UV/Vis/NIR studies were performed; 7 b was excluded from these studies owing to its low solubility (see above). In the case of mono‐oxidized [10]+, the UV/Vis/NIR studies showed no IVCT absorption, which is due to the resonance structure of 10 and hence the redox separation is ascribed to electrostatic interactions. On the contrary, mixed‐valent [5 b]+ and [12]+ showed IVCT absorptions, however, of low intensity, indicating weakly coupled systems according to the classification by Robin and Day, which is in good agreement with, for example, 2,7‐bispyrene.5 b]+ appeared together with LMCT. Compound [12]+ showed a more intense and narrow IVCT absorption, indicating a stronger metal–metal interaction than for 5 b. This might originate from the higher electron density at the Fc groups, owing to the electron‐donating OMe functionalities in positions 9 and 10 at phenanthrene. Furthermore, the IVCT transition of [12]+ was investigated in two different solvents, exploring its solvatochromic characteristics. A Δνmax shift of 1000 cm−1 was observed, confirming a class II classification according to Robin and Day.To confirm the metal–metal interaction in 5 a with 7 a, it becomes apparent that positions 1 and 6 at pyrene are favorable over positions 2 and 7. Moreover, the higher electron density of phenanthrene 12 bearing electron‐donating functionalities resulted in a more intense LMCT than in Fc2‐pyrene 5 b. These findings are in good agreement with, for example, ferrocenyl naphthalenes,In addition, within the spectroelectrochemical studies, LMCT transitions were observed that are shifted bathochromically depending on the characteristics of the substituents and the substitution pattern. Comparing the intensities of the LMCT transitions of 10 showed a complex solvation of the push–pull system, reflecting the solvent properties such as hydrogen‐bond donor capacity, polarizability, and solvation, resulting in a bathochromic shift of λmax.Solvatochromic studies on 5 b and SWCNTs was investigated by DFT calculations, which showed that the pyrene group of 5 b is oriented parallel to the CNT surface based on optimized π–π interactions. The adsorption behavior of 5 b is insignificantly influenced by the chirality or the diameter of the SWCNTs.The interaction between 5 b to interact non‐covalently with different SWCNTs ‐SWCNTs and semiconducting SWCNTs) was investigated by disentangling experiments. The debundeling with chirality‐enriched ‐SWCNTs was performed for different sonication protocols (see the Supporting Information). For one parameter set, the dispersions containing SWCNTs and 5 b in chloroform showed the typical S11 and the S22 transitions of disentangled SWCNTs in the UV/Vis/NIR spectra, which agree well with the reference spectra of a standard SWCNT dispersion, indicating a direct non‐covalent interaction between 5 b and the SWCNT sidewalls.Based on the DFT calculations, the ability of 5 b with semiconducting SWCNTS was studied (Gen2). As a result thereof, it was found that 5 b is able to disentangle SWCNTs as evident from the appearance of the S22 and S33 transitions in the UV/Vis/NIR spectra.With regard to the possible use of functionalized SWCNTs, integrated in CNT‐FETs, the interaction of 5 b in an exohedral fashion at the SWCNT sidewalls was proven by CV by using graphene paper as the working electrode, which showed a Fc/Fc+ redox event at 380 mV. This was further strengthened by the electrochemical investigations of solely 5 b, showing no ferrocenyl‐based redox processes. At a potential of 800 mV, the irreversible oxidation of the pyrene core occurred, resulting in polymerization and subsequent formation of polypyrene oligomers.The attachment of The debundeling and functionalization of SWCNTs by redox‐active Fc‐pyrenes in a non‐covalent manner is conceivable when using the 1,6‐substitution pattern at pyrene.5 b could be used in nanoelectronic application scenarios.Based on these findings, compound All synthesis procedures were performed under an atmosphere of argon with the solvents degassed prior to use. All reagents were obtained from commercial suppliers and used without further purification. The SWCNTs solid material was purchased from a commercial supplier ‐SWCNTs, batch number #MKB76336V) and used without further treatment. A commercial SWCNT dispersion, NanoIntegris IsoSol S‐100®, batch SP31‐176, was purchased from commercial suppliers and used without any further purification. Ferrocene boronic acid was synthesized from lithioferrocene1H and 125.7 MHz for 13C{1H} in the Fourier transform mode at ambient temperature. Chemical shifts are reported in δ (ppm) downfield from tetramethylsilane with the solvent as the reference signal . FTIR spectra were recorded by using a Thermo Nicolet IR 200 instrument. The melting points were determined with a Gallenkamp MFB 595 010 m melting point apparatus. Elemental analyses were performed by applying a Thermos FlashAE 1112 instrument. High‐resolution mass spectra were recorded with a Bruker Daltonite micrOTOF‐QII spectrometer . UV/Vis spectra between 210 and 1010 nm were recorded with a Carl Zeiss MCS 400 spectrometer utilizing CLD 300 (210–600 nm) and CLX 11 lamps (300–1010 nm). UV/Vis/NIR spectra of the SWCNT dispersions between 350 nm and 1300 nm were recorded by using a Shimadzu UV‐3100 PC absorption spectrometer on liquids in quartz cuvettes . For sonication, an Elmasonic P 30 H ultrasonic bath and a Bandelin KE76 tip sonotrode were used. Centrifugation of the dispersions was performed at a Sigma 3–30 K lab centrifuge in Oak Ridge tubes  with 10 mL nominal volume.NMR spectra were recorded with a Bruker Avance III 500 spectrometer operating at 500.3 MHz for 3, 5 a,b, 7 a,b, 10, and 12 (1.0 mmol L−1 [NnBu4][B(C6F5)4] as the supporting electrolyte) in dichloromethane were performed in a dried, argon‐purged cell at 25 °C. For the measurements, a three‐electrode cell containing a Pt auxiliary electrode, a glassy‐carbon working electrode (3.0 mm diameter), and an Ag/Ag+ (0.01 mmol L−1 [AgNO3]) reference electrode fixed on a Luggin capillary was used. The working electrode was pretreated by polishing it with a MicroFloc first with 1 μm and then with a 0.25 μm diamond paste. The reference electrode was constructed from a silver wire inserted in a 0.01 mmol L−1 [AgNO3] and a 0.1 mol L−1 [NnBu4][B(C6F5)4] acetonitrile solution in a Luggin capillary with a Vycor tip. This Luggin capillary was inserted into a second Luggin capillary containing a 0.1 mol L−1 [NnBu4][B(C6F5)4] dichloromethane solution and a Vycor tip. Experiments under the same conditions showed that all reduction and oxidation potentials were reproducible within ±5 mV. Experimental potentials were referenced against an Ag/Ag+ reference electrode, but the presented results are referenced against ferrocene as an internal standard as required by IUPAC.−1 decamethylferrocene (Fc*). Data were processed with a Microsoft Excel worksheet to set the formal reduction potentials of the FcH/FcH+ couple to 0.0 V. Under our conditions, the Fc*/Fc*+ couple appeared at −619 mV vs. FcH/FcH+, ΔEp=60 mV, whereas the FcH/FcH+ couple itself was at 220 mV vs. Ag/Ag+, ΔEp=61 mV.5 b@SWCNT (Gen2) nanoconjugates, a three‐electrode arrangement containing a Pt auxiliary electrode and an Ag/AgCl reference electrode (consisting of a silver wire covered with a thin film of AgCl) fixed in a glass tube (providing a pipetting controller for the supply of the electrolyte) at 25 °C was used.3[Fe(CN)6] (5 mm aqueous solution) in 1 m aqueous KCl solution (0.358 V).Electrochemical measurements of −1 solutions of 3, 5, 7 a, 10, 12, or 9‐ferrocenylphenanthrene in anhydrous dichloromethane containing 0.1 mol L−1 of [NnBu4][B(C6F5)4] as the supporting electrolyte were performed in an OTTLE ϵmax ±100 L mol−1 cm−1, νmax ±50 cm−1, and Δν1/2 ±50 cm−1.Spectroelectrochemical UV/Vis/NIR measurements of 2.0 mmol LKα radiation  or CuKα radiation  at 110 K by using oil‐coated shock‐cooled crystals. The structures were solved by direct methods and refined by full‐matrix least‐squares procedures on F2.Diffraction data were collected with an Oxford Gemini S diffractometer using graphite‐monochromated MoEads) of 5 b on CNT is calculated by Eads=E5 b/CNT−E5 b−ECNT, where E5 b/CNT, E5 b, and ECNT denote the total energies of the optimized structures of 5 b adsorbed on CNT, gaseous 5 b, and isolated CNT, respectively.Density functional theory (DFT) calculations were performed with periodic models by using the CASTEP code.2] (1 mol %), ferrocene boronic acid , K3PO4⋅H2O , and the respective aryl halide . Anhydrous toluene (15 mL) was added. The reaction mixture was stirred for 5 min at ambient temperature and then heated to reflux for 24 h. After cooling to ambient temperature, the reaction mixture was filtered through a pad of silica. Afterwards, all volatiles were removed by evaporation. Purification was realized by column chromatography  by using different dichloromethane/hexane mixtures (see below).A three‐necked 100 mL flask was charged with +; elemental analysis calcd for C26H17BrFe (465.16 g mol−1): C 67.13, H 3.68, found: C 67.69, H 4.76. Crystal data for 5 a: C26H17BrFe, Mr=465.15 g mol−1, monoclinic, I2/a, λ=0.71073 Å, a=18.4055(14) Å, b=7.4788(6) Å, c=26.788(2) Å, β=96.988(7)°, V=3659.9(5) Å3, Z=8, ρcalcd=1.688 mg cm−3, μ=3.016 mm−1, T=116.8(6) K, θ range 3.565–24.992°, 8764 reflections collected, 3199 independent reflections (Rint=0.0352), R1=0.0327, wR2=0.0701 (I>2σ(I)).Compound 5 b: Yield: 72.3 mg . M.p.: 176 °C (decomposition); 1H NMR (CDCl3): δ=4.22 , 4.49 , 4.84 , 8.02 , 8.10 , 8.39 , 8.73 ppm ; 13C NMR (CDCl3): δ=68.7 (C5H4), 69.9 (C5H5), 71.1 (C5H4), 87.6 , 124.1 (C16H8), 125.1 (C16H8), 125.4 (C16H8), 127.0 (C16H8), 129.0 (C16H8), 129.3 (C16H8), 129.7 (C16H8), 134.0 ppm (C16H8); IR (KBr): ν=2964 (m), 2925 (w), 2855 (w), 1601 (w), 1496 (w), 1456 (w), 1428 (w), 1409 (w), 1373 (w), 1262 (s), 1211 (w), 1105 (s), 1074 (s), 1022 (s), 881 (m), 866 (m), 854 (m), 804 (s), 684 (m), 668 cm−1 (m); HR‐MS (ESI‐TOF) m/z calcd for C36H26Fe2: 570.0729; found: 570.0734 [M]+; elemental analysis calcd for C36H26Fe2 (570.28 g mol−1): C 75.82, H 4.60; found: C 75.56, H 4.52. Crystal data for 5 b: C36H26Fe2, Mr=570.27 g mol−1, monoclinic, P21/n, λ=0.71073 Å, a=14.3748(18) Å, b=8.6113(9) Å, c=20.585(2) Å, β=105.022(12)°, V=2461.1(5) Å3, Z=4, ρcalcd=1.539 mg cm−3, μ=1.204 mm−1, T=116.95(10) K, θ range 3.043–24.996°, 5798 reflections collected, 5798 independent reflections (Rint=0.0655), R1=0.0771, wR2=0.1997 (I>2σ(I)).7 a was prepared according to the general synthetic methodology described above by using 2,7‐dibromopyrene . Compound 7 a was separated by column chromatography by using hexane/dichloromethane mixtures (v/v) starting from 9:1  to 4:1 (7 a). After evaporation of all volatiles, the received solid was recrystallized from acetone at −20 °C. Compound 7 a was isolated as an orange solid. Yield: 37 mg . M.p.: 223 °C; 1H NMR (CDCl3): δ=4.08 , 4.46 , 4.96 , 7.96 , 8.07 , 8.26 ppm ; 13C NMR (CDCl3): δ=67.2 (C5H4), 69.7 (C5H4), 70.0 (C5H5), 85.3 , 119.7 (C16H8), 123.1 (C16H8), 123.4 (C16H8), 123.5 (C16H8), 126.7 (C16H8), 127.3 (C16H8), 128.7 (C16H8), 131.1 (C16H8), 132.6 (C16H8), 138.0 ppm (C16H8); IR (KBr): ν=3036 (w), 2924 (w), 2852 (w), 1597 (s), 1554 (m), 1487 (m), 1429 (m), 1409 (m), 1299 (m), 1245 (s), 1217 (w), 1152 (m), 1145 (m), 1105 (s), 1037 (m), 1030 (m), 998 (s), 929 (m), 898 (m), 878 (s), 867 (s), 858 (s), 853 (s), 846 (s), 830 (s), 820 (s), 803 (s), 762 (s), 707 (s), 669 cm−1 (s); HR‐MS (ESI‐TOF) m/z calcd for C26H17BrFe: 463.9859; found: 463.9849 [M]+; elemental analysis calcd for C26H17BrFe (465.16 g mol−1): C 67.13, H 3.68; found: C 67.25, H 3.71. Crystal data for 7 a: C26H17BrFe, Mr=465.15 g mol−1, monoclinic, P21/c, λ=0.71073 Å, a=10.3922(8) Å, b=13.9915(11) Å, c=12.8138(11) Å, β=99.217(3)°, V=1839.1(3) Å3, Z=4, ρcalcd=1.680 mg cm−3, μ=3.001 mm−1, T=100 K, θ range 3.525–24.997°, 26 828 reflections collected, 3234 independent reflections (Rint=0.0982), R1=0.0268, wR2=0.0707 (I>2σ(I)).Compound 10 was synthesized in accordance with the general synthesis procedure described above by using 3,6‐dibromophenathren‐9,10‐dione . Compound 10 was separated by column chromatography  by using first hexane  and then dichloromethane/ethylacetate mixtures (v/v) of ratios 4:1 and 3:1 (10). After evaporation of all volatiles, compound 10 was obtained as a green solid. Yield: 136 mg . M.p.: 123 °C; 1H NMR (CDCl3): δ=4.13 , 4.55 , 4.86 , 7.56 , 8.05 , 8.15 ppm ; 13C NMR (CDCl3): δ=67.6 (C5H4), 70.3 (C5H5), 70.9 (C5H4), 83.0 , 120.6 (C14H6), 127.1 (C14H6), 129.0 (C14H6), 130.9 (C14H6), 136.0 (C14H6), 149.5 (C14H6), 180.1 ppm (CO); IR (KBr): ν=2959 (m), 2925 (s), 2854 (m), 1774 (w), 1658 (m), 1590 (s), 1465 (m), 1416 (m), 1262 (s), 1105 (s), 1029 (s), 924 (m), 807 (s), 731 cm−1 (m); elemental analysis calcd for C34H24Fe2O2 (576.25 g mol−1): C 70.87, H 4.20; found: C 70.76, H 4.11. Crystal data for 10: C35H26Cl2Fe2O2, Mr=661.16 g mol−1, monoclinic, P21/c, λ=0.71073 Å, a=10.1023(5) Å, b=38.6119(18) Å, c=13.9755(8) Å, β=93.989(5)°, V=5438.2(5) Å3, Z=8, ρcalcd=1.615 mg cm−3, μ=1.297 mm−1, T=129.9(4) K, θ range 3.023–25.999°, 34 953 reflections collected, 10 644 independent reflections (Rint=0.0537), R1=0.0819, wR2=0.1943 (I>2σ(I)).Compound m solution of tert‐butyllithium  in pentane was added dropwise at −30 °C to ferrocene  and KOtBu  dissolved in tetrahydrofuran (20 mL). After 1 h of stirring at this temperature, anhydrous [ZnCl2 2 thf]  was added in a single portion. The solution was kept for 1 h at −30 °C and an additional hour at 25 °C. Afterwards, [PdCl2(dppf)]  and the respective dibromoarenes  were added in a single portion and the reaction solution was stirred for 24 h at 60 °C. After evaporation of all volatiles, the precipitate was dissolved in dichloromethane (200 mL) and washed thrice with 100 mL portions of water. The organic phase was dried over MgSO4 and the solvent was removed under oil‐pump vacuum. The remaining solid was purified by column chromatography  by using different dichloromethane/hexane mixtures. All volatiles were removed under reduced pressure. The title compounds were obtained as solids.A 1.9 7 b was synthesized according to the general synthetic methodology for the Negishi C−C cross‐coupling protocol by using 2,7‐dibromopyrene . Compound 7 b was separated by column chromatography by using hexane/dichloromethane eluent mixtures (v/v) starting from 9:1  to 1:9 (7 b). The obtained solid was recrystallized from acetone at −20 °C. Compound 7 b was isolated as a red solid. Yield: 15 mg . M.p.: 265 °C (decomposition); 1H NMR (CDCl3): δ=4.08 , 4.45 , 4.96 , 8.04 , 8.24 ppm ; IR (KBr): ν=3116 (w), 3092 (w), 1606 (m), 1424 (m), 1407 (m), 1382 (m), 1103 (s), 1030 (s), 1000 (s), 932 (m), 881 (m), 829 (m), 806 (m), 714 (m), 668 cm−1 (w); elemental analysis calcd for C36H26Fe2 (570.28 g mol−1): C 75.82, H 4.60; found: C 76.63, H 4.43. Crystal data for 7 b: C36H26Fe2, Mr=570.27 g mol−1, monoclinic, P21/c, λ=1.54184 Å, a=11.0921(3) Å, b=7.8868(2) Å, c=14.2973(4) Å, β=100.294(2)°, V=1230.61(6) Å3, Z=2, ρcalcd=1.539 mg cm−3, μ=9.630 mm−1, T=100 K, θ range 4.051–65.912°, 11 449 reflections collected, 2128 independent reflections (Rint=0.0443), R1=0.0375, wR2=0.0961 (I>2σ(I)).Compound 11; 396 mg, 0.5 mmol). Compound 12 was separated by column chromatography by using hexane/dichloromethane eluent mixtures (v/v) starting from 9:1  to 1:9 (12). After evaporation of all volatiles, 12 was obtained as an orange solid. Yield: 100 mg . M.p.: 169 °C; 1H NMR (CDCl3): δ=4.10 , 4.12 , 4.43 , 4.86 , 7.80 , 8.16 , 8.68 ppm ; 13C NMR (CDCl3): δ=61.2 (OCH3), 67.0 (C5H4), 69.4 (C5H5), 69.9 (C5H4), 86.0 , 119.4 (C14H6), 122.3 (C14H6), 126.1 (C14H6), 127.8 (C14H6), 128.5 (C14H6), 136.9 ppm (C14H6); IR (KBr): ν=2925 (s), 2854 (s), 1744 (m), 1700 (m), 1684 (m), 1653 (m), 1607 (s), 1559 (m), 1540 (m), 1507 (m), 1458 (s), 1446 (s), 1419 (m), 1337 (m), 1311 (s), 1189 (m), 1105 (s), 1092 (s), 1061 (s), 1027 (m), 983 (s), 885 (m), 874 (s), 707 (w), 668 (w), 661 cm−1 (w); elemental analysis calcd for C36H30Fe2O2 (606.32 g mol−1): C 71.31, H 4.99; found: C 70.50, H 4.89. Crystal data for 12: C36H30Fe2O2, Mr=606.30 g mol−1, orthorhombic, Pnn2, λ=1.54178 Å, a=19.680(2) Å, b=6.3428(8) Å, c=10.6327(17) Å, V=1327.3(3) Å3, Z=2, ρcalcd=1.517 mg cm−3, μ=9.021 mm−1, T=100(2) K, θ range 4.493–64.897°, 23 836 reflections collected, 2100 independent reflections (Rint=0.1099), R1=0.1412, wR2=0.4059 (I>2σ(I)).The title compound was prepared according to the general synthesis protocol for the Negishi C−C cross‐coupling by using 3,6‐dibromo‐9,10‐dimethoxyphenanthrene (Master5 b was prepared by dissolving 5 b (1.86 mg) in chloroform . Afterwards, the obtained solution was treated by bath sonication  for 10 min.The master solution Master5 b (800 μL) in chloroform .The mixture FC00 was obtained by diluting The mixture FC01 was prepared by dispersing SWCNTs solid material (0.82 mg) in FC00 (6 mL) and applying bath sonication  for 30 min, followed by centrifugation .The mixture FC02 was prepared by dispersing SWCNTs solid material (0.75 mg) in FC00 (6 mL) and applying tip sonication  for 30 min, followed by centrifugation .−1.Dispersions FC01 and FC02 were prepared with a SWCNT solid content of (0.128±0.009) mg mL3) was obtained by pouring SWCNTs into CHCl3 and employing bath sonication  for 30 min followed by centrifugation . The SWCNT solid content was kept to (0.128±0.009) mg mL−1.The reference dispersion SWCNTs (CHCl2O) was obtained by adapting previously reported sonication procedures.−1.The reference dispersion of SWCNTs (HH‐fluoren‐2‐yl)aryl‐based polymer (PFH‐R)5 b dissolved in toluene  to attach 5 b at those parts of the SWCNT sidewalls depleted from PFH‐R. To apply UV/Vis/NIR analysis for this step, the bucky paper obtained this way was manually delaminated from the filter by using standard lab cutlery. The slices of the SWCNT solid were then collected in a new glass vial (10 mL screw‐cap) and re‐dispersed in toluene (2 mL) by using a bath sonicator . The obtained liquid obtained by this procedure (Gen2) was subjected to the UV/Vis/NIR analysis and compared with basic spectra of 5 b in toluene, just diluted NanoIntegris IsoSol S‐100® (Gen0) and a reference sample obtained directly by dissolving a bucky paper derived from NanoIntegris IsoSol S‐100® without the washing (toluene) and flushing (5 b in toluene) steps (Gen1).The commercial SWCNT dispersion, stabilized by a 9‐ for all new compounds are given. This material is available free of charge via the Internet. CCDC https://www.ccdc.cam.ac.uk/services/strctures?id=doi:10.1002/chem.201904450 contain the supplementary crystallographic data for this paper. These data are provided free of charge by http://www.ccdc.cam.ac.uk/.Additional structural data, cyclic voltammograms, square wave voltammograms, and UV/Vis/NIR spectra as well as spectroscopic details  should be addressed to the authors.SupplementaryClick here for additional data file.


In contrast, 1,7‐bis(1‐phospholano)heptane (1b) formed coordination polymers 4a (Cl) and 4b (Br) with bridging bis‐phospholane and halido ligands. A unique paddle wheel‐type metallacryptand structure 5 was obtained from 1a and silver(I) bromide in a 2:3 reaction (M:L). All complexes were fully characterized by NMR, IR spectroscopy, mass spectrometry, and X‐ray crystallography.In a 2:2 reaction with silver(I) chloride or bromide, 1,5‐bis(1‐phospholano)pentane ( John Wiley & Sons, Ltd. Grüttner and Krause. They synthesized 1‐phenylphospholane by reacting the di‐Grignard reagent of 1,4‐dibromobutane with dichlorophenylphosphine.Brunner et al. published the synthesis of the chiral 3,4‐disubstituted correspondent.Wilson et al.Burk et al.Baccolini et al.H‐phospholane and P‐substituted phospholanes can be obtained using this method. In 2009, the same group reported the successful synthesis of chiral alkylphospholanes.Phospholanes are five‐membered cyclic phosphines with good σ‐donor properties, which make them especially interesting as ligands in transition metal catalysis. Their ring structure and well‐defined geometry are key features, which set them apart from other phosphines.Burk and co‐workers.Burk published a paper entitled “Modular Phospholane Ligands in Asymmetric Catalysis”, which shows the ten‐year development of ligands based on the trans‐2,5‐disubstituted phospholane moiety.Clark and Landis comprehensively summarized the following developments in this field.The real success story of the phospholane ligands started, however, in 1990 with the synthesis of bis‐phospholanoethane (BPE) and DuPhos by cis complexes with catalytically active metals.Emrich and Jolly,Oisaki et al.4 as a metal complex precursor.3CN)4]BF4.These chiral bis‐phospholanes are usually based on rigid spacers that allow them to act as chelate ligands forming 1a)1b)We have performed an in‐depth study of the coordination behavior of these flexible bis‐phospholane ligands in silver(I) halide complexes and report here the synthesis, characterization, and structural elucidation of complexes based on 1,5‐bis(1‐phospholano)pentane (1a)31P{1H} NMR spectrum of the crude reaction mixture showed the expected downfield shift from the free ligands (ca. –27 ppm)2 and 3 suitable for X‐ray structure analysis were obtained at room temperature by slow diffusion of n‐hexane into a DCM/toluene solution. The results showed two different coordination modes: A metallacycle 2 with intramolecular chlorido bridges  (Table 2 [245.5(2) and 245.7(2) pm] which are more than 8 pm longer than those in the corresponding AgBF4 complex.2Cl2 moiety forms an almost perfect square as shown by Ag–Cl bond lengths of 271.1(2) and 270.9(2) pm and a Cl1–Ag1–Cl1' bond angle of 90.00(5)°. A similar structure was reported for the 2:2 complexes of 1,5‐bis(diphenylphosphanyl)pentane (dpppn) with AgX  by Effendy et al.Cassel.2, which is to be expected given the electron‐withdrawing effect of the phenyl groups of the triphenylphosphine.Complex 31P{1H} NMR spectrum of complex 2 in CDCl3 shows a singlet at δ = –5.7 ppm. Coupling with the NMR‐active silver isotopes 107Ag (NA = 51.84 %) or 109Ag  is not observed. The lack of coupling in solution at room temperature was also observed by Streitberger et al.Effendy and co‐workers who carried out more thorough NMR studies on silver(I) bis(diphenyl)phosphine complexes.2 in solution is evidenced by the ESI(+) mass spectrum which showed the [M–Cl]+ molecular ion at m/z = 739.1.The 3 crystallizes in the monoclinic space group C2/c with four molecules in the unit cell. The solid‐state structure shows two molecules of 1,5‐bis(1‐phospholano)pentane bridging two silver(I) cations forming a frame‐like macrocycle   and 237.02(8) pm but a significantly larger P–Ag–P bond angle of 176.89(1)° for a distinct frame‐like structure obtained using AgBF4  cations of neighboring metallamacrocycles interact with an additional AgBr moiety, thus forming Ag3Br3 assemblies  phosphine complexes. Often they form tetrameric cubane‐like structures (Ag4Br4), when simple monodentate phosphine ligands are employed.Effendy et al. reported a tetranuclear 2:1 complex , which is formed when AgX and bis(diphenylphosphanyl)methane (dppm) are reacted in a 2:1 ratio. The structure of the complex includes an Ag4Br4 assembly with a “step” conformation.Schubert et al. found that dppm and AgBr can also form a 3:3 complex bearing an [Ag3Br2]+ cluster, while bis(diphenylphosphanyl)methylamine (dppa) forms a dimeric 2:4 complex in which an [Ag4Br2]2+ octahedron is present.3Br3 assembly to the one found in complex 3 was assumed to bridge adjacent macrocycles in a silver(I) complex based on 2,5‐bis(diphenylphosphinomethyl)thiophene (dpmt). However, only the crystal structure of the iodine homologue was reported.3 shows that Ag3Br3 bicycles are bridged by a set of two 1,5‐bis(1‐phospholano)pentane ligands, building a polymeric chain along (101) .Ag31P{1H} NMR spectrum of complex 3 in CDCl3 shows a singlet at δ = –8.5 ppm. The ESI(+) mass spectrum showed peaks at m/z = 1590.6, 1402.8, 1158.7, and 1215.0, corresponding to the fragments [M+L+2Ag+Br]+, [M+L+Ag]+, [M+Ag]+, and [3 L+3Ag+2Br]+, respectively. The peaks at m/z = 970.9 (base peak) and 780.0 corresponding to fragments [M–Br]+ and [M–AgBr2]+, respectively, are proof that the frame‐like metallamacrocycle is stable in solution .The 1b)1a. The reaction mixtures were shielded from light. After stirring at room temperature for four hours, the 31P{1H} NMR spectra of the crude reaction mixture showed the expected downfield shift with signals around –7 ppm. Crystals of the final products 4a and 4b  are marginally shorter than in complex 2. One of the Ag–Cl bonds (Ag1–Cl2) is ca. 6 pm shorter than the one in 2, causing the Ag2Cl2 ring to slightly deviate from the ideal square arrangement, with angles ranging from 85.54(4) to 93.24(3)° (Table Ag–P bond lengths in 4a forms a (001) layer structure in which the silver(I) cations are linked in series by chlorine atoms, while the bis‐phospholane ligands are arranged in a zigzag fashion. The layers are formed by two distinct interwoven polymeric chains  mass spectrum showed the base peak at m/z = 795 corresponding to the fragment [L2Ag2Cl]+ (L = ligand 1b).The 4b crystallizes in the monoclinic space group P21/c. The solid‐state structure  layer  to 138.70(3)°, Table 3 alkane ligands when comparing open macrocycles [P–Ag–P 144.30(7)°] to species in which halido bridging was observed [P–Ag–P 131.24(9)°].4b + (L = ligand 1b). Two other peaks corresponding to species with higher m/z values were observed but could not be attributed and probably correspond to oligomeric fragments.The 1a,1b and two equivalents of AgBr were performed under similar conditions as described for the 1:1 reactions. The 31P{1H} NMR spectrum of the crude reaction mixtures showed, in each case, one downfield‐shifted broad singlet. Suitable crystals for X‐ray structure analysis were obtained at room temperature by layering a DCM/toluene (for ligand 1a) or DCM (for ligand 1b) solution of the crude product with n‐hexane. X‐ray structure analysis showed that in the case of ligand 1b the same coordination polymer 4b was formed as in the 1:1 reaction, while ligand 1a yielded the metallacryptand 5  cations are bridged by three 1,5‐bis(1‐phospholano)pentane ligands in a trigonal‐planar fashion forming a triangular prism (paddle wheel) with Ag–P distances ranging from 241.88(9) to 251.48(9) pm and P–Ag–P angles ranging from 104.74(3) to 137.51(3)°  and 248.5(1) pm, respectively]. Ag–Br bond lengths [278.90(4) and 281.84(5) pm] are comparable to those previously observed in 4b.Complex 31P{1H} NMR studies reported by Dean et al. (1987) and later by Peringer et al. (1988) postulated the formation of complexes [Ag2(μ‐dppm)3](AsF6)22(μ‐dppm)3](CF3SO3)2,Hong et al. published the structure of [Ag2(μ‐dppm)3](NO3)2 and revealed its paddle wheel topology.5 is not only the first such example bearing bis‐phospholane ligands but also the first silver(I) bis‐phosphine paddle wheel‐type metallacryptand.Silver(I) complexes with an M:L ratio of 2:3 and with bridging bis(phosphanyl)alkane ligands are rare. 1a) and 1,7‐bis(1‐phospholano)heptane (1b), gave macrocycles, coordination polymers and paddle wheel‐type metallacryptands depending on the stoichiometry, length of alkylene spacer (C5 or C7) and counter anion. These complexes are further proof that these simple and highly flexible bis‐phospholane ligands have extremely versatile coordination properties.The reaction of silver(I) chloride or bromide with two highly flexible bis‐phospholane ligands, 1,5‐bis(1‐phospholano)pentane (1b)δ) of 1H, 13C, and 31P are reported in parts per million (ppm) at 400.12, 100.63, and 162.02 MHz, respectively, with tetramethylsilane as internal standard and referencing to the unified Ξ scale.J are given in Hertz. The numbering scheme for assignment of 1H NMR spectra is given in Scheme –1. Wavenumbers ν̃ are reported in cm–1. Mass spectra were recorded with an ESQUIRE 3000 plus spectrometer. Elemental analyses were carried out with a Heraeus VARIO EL oven. Melting points were measured in sealed capillaries by using a variable heater from Gallenkamp.All reactions and crystallization of compounds were carried out in a nitrogen atmosphere by using standard Schlenk techniquesSynthesis of Bisdisilver(I) dichloride (2): AgCl  was added as a solid to a stirred solution of 1a  in 10 mL DCM. The Schlenk flask was immediately wrapped in aluminum foil and the reaction mixture was stirred at room temperature for 4 h, filtered and all volatiles were removed in vacuo. Afterwards, the white residue was washed with n‐hexane (3 × 2 mL) to yield 2  as a white solid. Crystals suitable for single‐crystal X‐ray diffraction were obtained from a DCM/toluene mixture layered with n‐hexane at room temperature. M.p. 129 °C. 1H NMR (CDCl3): δ = 2.19–2.03 , 1.92–1.72 , 1.72–1.59 , 1.50–1.48 ppm . 13C{1H} NMR (CDCl3): δ = 32.3–32.0 , 28.0–27.9 , 27.2 (s), 27.1–26.9 , 26.3–25.7 ppm . 31P{1H} NMR (CDCl3): δ = –5.7 ppm (s). IR: ν̃ = 2937 , 2915 , 2855 , 1455 , 1436 , 1113 (w), 843 (w), 689 cm–1 (w). MS (ESI(+), DCM/acetonitrile): m/z = 739.1 [M–Cl]+, 597.2 [AgL2]+, 351.1 [AgL]+; L = 1a. C26H52Ag2Cl2P4: calcd. C 40.28, H 6.76 %; found C 40.29, H 6.82 %.Synthesis of Poly{bistrisilver(I) tribromide} (3): AgBr  was added as a solid to a stirred solution of 1a  in 10 mL DCM. The Schlenk flask was immediately wrapped in aluminum foil and the reaction mixture was stirred at room temperature for 4 h, filtered and all volatiles were removed in vacuo. Afterwards the white residue was washed with n‐hexane (3 × 2 mL) to remove excess ligand, yielding 3  as a white solid. Crystals suitable for single‐crystal X‐ray diffraction were obtained from a DCM solution layered with n‐hexane at room temperature. M.p. 195 °C. 1H NMR (CDCl3): δ = 2.20–2.04 , 1.91–1.76 , 1.75–1.55 ppm . 13C{1H} NMR (CDCl3): δ = 27.6–27.3 , 27.1 (s), 26.3–26.0 , 26.0–25.8 ppm . 31P{1H} NMR (CDCl3): δ = –8.5 ppm (s). IR: ν̃ = 2934 , 2919 , 2845 , 1444 , 1407 , 1112 (w), 1023 (w), 845 (w), 708 cm–1 (w). MS (ESI(+), DCM/MeOH): m/z = 1590.6 [M+L+2Ag+Br]+, 1402.8 [M+L+Ag]+, 1158.7 [M+Ag]+, 1215.0 [Ag3L3Br2]+, 970.9 [M–Br]+, 780.0 [M–AgBr2]+; M = [Ag3L2Br3], L = 1a. C26H52Ag3Br3P4: calcd. C 29.69, H 4.98 %; found C 29.66, H 5.01 %.Synthesis of Poly{bissilver(I) chloride} (4a): AgCl  was added as a solid to a stirred solution of 1b  in 10 mL DCM. The Schlenk flask was immediately wrapped in aluminum foil and the reaction mixture stirred at room temperature for 4 h, filtered and all volatiles were removed in vacuo. Afterwards the white residue was washed with n‐hexane (3 × 2 mL) to yield 4a  as a white solid. Crystals suitable for single‐crystal X‐ray diffraction were obtained from a DCM/THF mixture layered with n‐hexane at room temperature. M.p. 103 °C. 1H NMR (CDCl3): δ = 2.12–1.99 , 1.85–1.66 , 1.64–1.53 , 1.51–1.14 . 13C{1H} NMR (CDCl3): δ = 31.1–30.5 , 29.2 (s), 28.3–27.8 , 27.2 (s), 27.1–26.8 , 26.3–25.8 ppm . 31P{1H} NMR (CDCl3): δ = –5.3 ppm (s). IR: ν̃ = 2962 , 2927 , 2856 , 1446 , 1261 (s), 1105 (s), 1024 (s), 802 (s), 720 cm–1 (w). MS (ESI(+), DCM/MeOH): m/z = 795.0 [Ag2L2Cl]+, 651.0 [AgL2]+, 379.0 [AgL]+; L = 1b. C15H30AgClP2: calcd. C 43.34, H 7.27 %; found C 43.30, H 7.21 %.Synthesis of Poly{bissilver(I) bromide} (4b): AgBr  was added as a solid to a stirred solution of 1b  in 10 mL DCM. The Schlenk flask was immediately wrapped in aluminum foil and the reaction mixture was stirred at room temperature for 4 h, filtered and all volatiles were removed in vacuo. Afterwards the white residue was washed with n‐hexane (3 × 2 mL) to yield 4b  as a white solid. Crystals suitable for single‐crystal X‐ray diffraction were obtained from a DCM solution layered with n‐hexane at room temperature. M.p. 150 °C. 1H NMR (CDCl3): δ = 2.22–2.09 , 1.94–1.74 , 1.70–1.60 , 1.54–1.22 ppm . 13C{1H} NMR (CDCl3): δ = 31.0–30.2 , 29.1 (s), 28.4–27.7 , 27.3 (s), 27.1–26.7 , 26.5–25.8 ppm . 31P{1H} NMR (CDCl3): δ = –5.7 ppm (s). IR: ν̃ = 2931 , 2852 , 1447 , 1400 , 1113 (w), 846 cm–1 (w). MS (ESI(+), chloroform/MeOH): m/z = 839.1 [Ag2L2Br]+, 381.1 [AgL]+; L = 1b. C15H30AgBrP2: calcd. C 39.16, H 6.57 %; found C 39.23, H 6.65 %.Synthesis of Trisdisilver(I) Dibromide (5): AgBr  was added as a solid to a stirred solution of 1a  in 10 mL DCM. The Schlenk flask was immediately wrapped in aluminum foil and the reaction mixture stirred at room temperature for 4 h, filtered and all volatiles were removed in vacuo. Afterwards the white residue was washed with n‐hexane (3 × 2 mL) to yield 5  as a white solid. Crystals suitable for single‐crystal X‐ray diffraction were obtained from a DCM/toluene mixture layered with n‐hexane at room temperature. M.p. 139 °C. 1H NMR (CDCl3): δ = 2.18–2.05 , 1.94–1.81 , 1.79–1.68 , 1.60–1.48 , 1.45–1.38 ppm . 13C{1H} NMR (CDCl3): δ = 34.0–33.4 , 29.3 (s), 27.9 , 27.4 (s), 27.0 ppm . 31P{1H} NMR (CDCl3): δ = –9.1 ppm (s). IR: ν̃ = 2921 , 2855 , 1447 , 1409 , 1109 (w), 1069 (w), 848 cm–1 (w). MS (ESI(+), DCM/MeOH): m/z = 783.0 [Ag2L2Br]+, 595.2 [AgL2]+; L = 1a. C39H78Ag2Br2P6: calcd. C 42.26, H 7.09 %; found C 42.28, H 7.04 %.Crystal Structure Determinations: The data were collected on a Gemini diffractometer (Rigaku Oxford Diffraction) using Mo‐Kα radiation (λ = 71.073 pm) and ω‐scan rotation. Data reduction was performed with CrysAlisPro2: SHELXS‐97;4a: SIR‐923, 4b, 5: SHELXT‐20144a, all structures are disordered to a certain extent. Mostly the five‐membered C4H8P ring was disordered, and for 3 and 4b some of the CnH2n chains were disordered as well. Details concerning data collection and crystallographic details are summarized in Table 2), CCDC‐1974714 (3), CCDC‐1974716 (4a), CCDC‐1974717 (4b), and CCDC‐1974715 (5) .Crystallographic data for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies of the data can be obtained free of charge on quoting the depository numbers CCDC‐1974713 (Supporting Information (see footnote on the first page of this article): 1H, 13C{1H}, 31P{1H} NMR, IR and mass spectra (ESI(+)) of complexes 2, 3, 4a, 4b and 5, and 31P{1H} NMR spectrum of the reaction mixture of 1a with AgBr, ratio 3:2.https://doi.org/10.1002/zaac.202000001 or from the author.Supporting information for this article is available on the WWW under Supporting InformationClick here for additional data file.


A symmetrical dicarbonohydrazide was used to synthesize a centrosymmetric tetranuclear zinc(II) complex in which two of the zinc cations are pentacoordinated and the other two are hexacoordinated. II complex, [Zn4(C13H11N6O)2Cl6(H2O)2] or {[Zn2(HL)(H2O)(Cl2)](μCl)2[Zn2(HL)(H2O)(Cl)]}2, was synthesized by mixing an equimolar amount of a methanol solution containing ZnCl2 and a methanol solution containing the ligand H2L . In the tetranuclear complex, each of the two ligand molecules forms a dinuclear unit that is connected to another dinuclear unit by two bridging chloride anions. In each dinuclear unit, one ZnII cation is pentacoordinated in a N2OCl2 in a distorted square-pyramidal geometry, while the other ZnII cation is hexacoordinated in a N3OCl2 environment with a distorted octahedral geometry. The basal plane around the pentacoordinated ZnII cation is formed by one chloride anion, one oxygen atom, one imino nitrogen atom and one pyridine nitrogen atom with the apical position occupied by a chloride anion. The basal plane of the hexacoordinated ZnII cation is formed by one chloride anion, one hydrazinyl nitrogen atom, one imino nitrogen atom and one pyridine nitrogen atom with the apical positions occupied by a water oxygen atom and a bridged chloro anion from another dinuclear unit, leading to a tetranuclear complex. A series of intramolecular C—H⋯Cl hydrogen bonds is observed in each tetranuclear unit. In the crystal, the tetranuclear units are connected by intermolecular C—H⋯Cl, C—H⋯O and N—H⋯O hydrogen bonds, forming a planar two-dimensional structure in the ac plane.A tetranuclear Zn S-cis or S-trans, yielding different structures with the same metal cation. These ligands can coordinate to transition metals in a pentadentate or hexadentate manner  complex 4](NO3)4·2H2O where H2L1 is 1,5-bis[1-(pyridin-2-yl)ethylidene)carbonohydrazide]. The study of the fluorescence properties of the ligand H2L1 and its complex revealed that complexation increased the fluorescent properties of the ligand (H2O)(Cl2)](μCl)2[Zn2(HL)(H2O)(Cl)]}2 where H2L is 1,5-bis(pyridin-2-ylmethylene)carbonohydrazide.The behavior of these molecules has attracted the interest of chemists working in coordination chemistry. The free dicarbonohydrazide exhibits biological activities /60 where β and α are the largest values of the bond angles around the central atom]; τ = 0 for a perfect square pyramidal geometry while τ = 1 for a perfect trigonal–bipyramidal geometry. In the case of the title complex, the τ value of 0.1085 is indicative of a distorted square-pyramidal geometry around the Zn1 center. The equatorial plane is occupied by atoms N5, N6, Cl3, O2 while the apical position is occupied by Cl2. The angles N5—Zn1—O2 [72.76 (9)°], O2—Zn1—Cl3 [96.00 (6)°], Cl3—Zn1—N6 [97.10 (8)°] and N6—Zn1—N5 [75.82 (10)°] deviate from those for a regular square pyramid. The transoid angles in the basal plane O2—Zn1—N6 and N5—Zn1—Cl3 deviate severely from linearity with values of 144.87 (10) and 138.36 (8)°, respectively –111.20 (7)° and transoid angles of 171.67 (8)° [N2—Zn2—Cl1] and 148.24 (10)° [N4—Zn2—N1]. The sum of the angles subtended by the atoms in the plane is 359.77°. The apical positions are occupied by O1 and Cl1i with O 1—Zn2—Cl1i = 172.20 (7)° ° is in accordance with the value reported for the complex di-μ-chlorido-bis{[2-({[2-(2-pyridyl)ethyl](2-pyridylmethyl)amino}methyl)-phenol]zinc(II)} bis(perchlorate) dihydrate  and 2.7489 (10) Å, respectively, agree with those for a chloride anion in a bridging position  or diprotonated (H4L2+) and additionally one Dy complex molecule in which HL− and L2− are present as ligands. Among the diprotonated molecules, three different counter-ions are present: I− in AVOSOV : 3439, 3204, 3198, 3055, 2936, 1684, 1582, 1610, 1582, 1532, 1467, 1360, 1274, 1131. 1H NMR : 7.6–8.72 ; 10.82 ; 8.03 . 13C NMR : 157.9 (C=O); 154.70 (CPy); 148.07 (CPy); 146.67 (C=N) imine; 137.60 (CPy); 123.00 (CPy); 119.09 (CPy).Carbonohydrazide  was introduced into a 100 mL flask containing 20 mL of methanol. To the resulting suspension was added a methanolic solution containing 2-pyridinecarbaldehyde (4.757 g 44.4 mmol) and two drops of glacial acetic acid. The mixture was stirred under reflux for 2 h. After being kept for two days at 277 K, the resulting orange solution yielded a precipitate, which was recovered by filtration. The solid was washed successively with cold methanol (2 × 10 mL) and diethyl ether (2 × 10 mL) before being dried under PSynthesis of the title complex2L  in 10 mL of methanol and a methanolic solution of ZnCl2 . A yellow solution was obtained after stirring for 1 h at room temperature. The solution was filtered, and the filtrate left for slow evaporation. After two weeks, yellow crystals suitable for X-ray diffraction were collected, yield 87.9%. Analysis calculated for [C26H26Cl6Zn4N12O4] C, 29.89; H, 2.51; N, 16.09. Found: C, 29.88; H, 2.49; N, 16.05. ΛM (S cm2 mol−): 11. IR (cm−1): 3428, 3116, 3043, 1585, 1553, 1497, 1461, 1377, 1313, 1226, 1143, 820.The title complex was prepared by mixing a solution of HUiso(H) = 1.2Ueq(N) or 1.5Ueq(O). C atoms were placed in calculated positions and refined as riding with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989020009834/ex2035sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020009834/ex2035Isup2.hklStructure factors: contains datablock(s) I. DOI: 2011426CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-019-45003-7, published online 14 June 2019Correction to: The Supplementary Information file originally published with this Article contained errors.In the ‘Detailed experimental procedures:’ section,“106.57 (c-2’)”now reads:“10657 (C-2’)”and“mp 91–92 °C”now reads:“m.p. mp 91–92 °C”.Finally, the original file contained tracked changes.These errors have been corrected in the Supplementary Information that now accompanies the Article.


To the Editor,Colorectal cancer (CRC) is a malignance ranking the third cause of death in malignant tumors.P value = 7.458 × 10−18) and indicated a favorable prognosis in patients with CRC (P = .016), which was inconsistent with our general understanding in other type of cancers , −0.71 (P = 8 × 10−57), and 0.71 (P = 1 × 10−55), respectively    showed that CCDC80 expression level was independent predictive factor  Figure . Kaplan‐) Figure . The RNA) Figure .To explore the relationship between the drugs sensitivity and CCDC80 expression, the Genomics of Drug Sensitivity in Cancer database was utilized to analyze the correlation coefficient of CCDC80 level and IC50 of multiple drugs Figure . To our Next, we overexpressed CCDC80 in Lovo cells by lentivirus infection and validated by RT‐PCR Figure . ConsistP = 5.32 × 10−02), dendritic cells (P = 7.04 × 10−40), macrophage cells (P = 3.52 × 10−56), CD4+ T cells (P = 8.64 × 10−29), CD8+ T cells (P = 4.14 × 10−08), and neutrophil cells (P = 3.34 × 10−28)  Figure . Furthern Figure . Among tThe authors declare no conflict of interest.Guangci Distinguished Young Scholars Training Program; Grant Number: GCQN‐2019‐B17.Yu‐Jun Dai, Da‐Wei Wang, and Ling‐Ling Shu designed the concept and experiments. Wei‐Da Wang, Kun‐Hao Bai, and Guo‐Yan Wu performed the experiments; Wei‐Da Wang, Si‐Yuan He, Xin Huang, Qian‐Yi Zhang, Pei‐Dong Chi, and Liang Li collected the data and did the analysis. Wei‐Da Wang, Yu‐Jun Dai, and Guo‐Yan Wu prepared the manuscript draft. Yu‐Jun Dai and Da‐Wei Wang provided research support and revised the manuscript. All the authors approved the final proof.figureS1Click here for additional data file.figureS2Click here for additional data file.tableS1Click here for additional data file.tableS2Click here for additional data file.tableS3Click here for additional data file.tableS4Click here for additional data file.Supporting informationClick here for additional data file.


The structure is composed of cation–oxygen bilayers, which are surrounded by hydrophobic methylethyl chains on both sides. Stacking of these sandwiches forms the structure. The potassium cations are situated in an irregular coordination polyhedron composed of seven O atoms.The structure of poly[bis(μ 2(C4H7O2)2(H2O)]n, is composed of stacked sandwiches, which are formed by cation–oxygen bilayers surrounded by methylethyl hydrophobic chains. These sandwiches are held together by van der Waals interactions between the methylethyl groups. The methylethyl groups are disordered over two positions with occupancies 0.801 (3):0.199 (3). The potassium cations are coordinated by seven O atoms, which form an irregular polyhedron. There is a water molecule, the oxygen atom of which is situated in a special position on a twofold axis (Wyckoff position 4e). The water H atoms are involved in Owater—H⋯Ocarboxyl hydrogen bonds of moderate strength. These hydrogen bonds are situated within the cation–oxygen, i.e. hydrophilic, bilayer.The structure of the title compound, [K These sandwiches are bonded by van der Waals forces.In all of these structural types, water molecules can occur; examples are given in Table 1M+CnHn+12COO−, n > 2, as follows from the known structures of Li(C3H5O2) , catena-[(μ2-propanoato)thallium(I)(propanoato)thallium(I)]  have been reviewed. The motif of stacked layers, however, seems to be typical for simple alkali alkanoates Thus, the typical motif of separated hydrophobic and hydrophilic parts of the molecules can be generalized for carboxylates other than formates and acetates.nHn+12COO−, n > 2, hinder possible applications of these compounds, although there are some exceptions such as lanthanide zinc butyrates or their analogues, which have been applied for the synthesis of lanthanide–zinc–oxygen nanoparticles  1 − x, y, z; (ii) x, −y, z; (iii) x, y, z; (iv) x, −1 + y, z.) It is also worth mentioning that the distances between the cation and the oxygen atoms belonging to the same carboxylate are quite different: K1—O1 = 3.1113 (13) Å and K1—O2 = 2.8056 (13) Å.The structural unit of the title compound is shown in Fig. 1The prominent feature of the title structure is the presence of an oxygen–metal bilayer, which is surrounded by methylethyl chains on both sides Fig. 2. This biwater—H⋯Ocarboxylate hydrogen bonds of moderate strength  and 3.01 (2) Å, respectively, see Fig. 3v, the bond valence of which is 0.0385 (1) 6  = 105.00 (1)° while Uiso(H1O3) = 1.5Ueq(O3). A trial refinement showed that the water oxygen was fully occupied. The C1—C2, C1—C2a bonds were restrained to be equal [1.540 (1) Å] as were C2—C3, C2—C3a and C2—C4, C2—C4a [1.500 (1) Å]. These values were found to yield the lowest R factors. Moreover, angle restraints to C3—C2—C4 and C3a—C2a—C4a were also applied. Of course, these C—C distances are affected by a large thermal agitation and are less reliable, as are the geometric parameters, compared to those of atom C1.The methanetriyl hydrogens H110.1107/S2056989020012591/dj2009sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020012591/dj2009Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020012591/dj2009Isup3.smiSupporting information file. DOI: 2032320CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


We performed batch incubation experiments with an anammox-dominated biomass to investigate nitrogen (N) and oxygen (O) isotopic fractionation factors during anammox and also examined apparent isotope fractionation factors during anammox in an actual wastewater treatment plant. We conducted one incubation experiment with high δ18O of water to investigate the effects of water δ18O. The N isotopic fractionation factors estimated from incubation experiments and the wastewater treatment plant were similar to previous values. We also found that the N isotopic effect (15εNXR of –77.8 to –65.9‰ and 15ΔNXR of –31.3 to –30.4‰) and possibly O isotopic effect (18εNXR of –20.6‰) for anaerobic nitrite oxidation to nitrate were inverse. We applied the estimated isotopic fractionation factors to the ordinary differential equation model to clarify whether anammox induces deviations in the δ18O vs δ15N of nitrate from a linear trajectory of 1, similar to heterotrophic denitrification. Although this deviation has been attributed to nitrite oxidation, the O isotopic fractionation factor for anammox is crucial for obtaining a more detailed understanding of the mechanisms controlling this deviation. In our model, anammox induced the trajectory of the δ18O vs δ15N of nitrate during denitrification to less than one, which strongly indicates that this deviation is evidence of nitrite oxidation by anammox under denitrifying conditions.Isotopic fractionation factors against  However, they lacked information on the 18O fractionation factor for anammox, and assumed that the 18O fractionation factor during NO3– production by anammox was similar to that for aerobic nitrite oxidation to NO3– by nitrifiers (nitrification). Thus, it is essential to investigate the 15N and 18O fractionation factors during anammox not only for the better use of the δ18O and δ15N of NO3– in anammox studies, but also to obtain a more detailed understanding of 15N and 18O fractionation.Studies on 18O fractionation factors during anammox. We calculated apparent 15N and 18O fractionation factors with data collected from a wastewater treatment plant (WWTP) at which anammox reactors were installed at the final stage of treatment .In the first experiment (Experiment A), the biomass in the reactor was sampled and incubated with the media used for the reactor, while the sampled biomass was re-suspended in fresh, chemically defined media in the second (Experiment B) and third (Experiment C) experiments. Difficulties were associated with performing incubation experiments with the anammox biomass for isotopic measurements, and, thus, we employed slightly different settings and operations to facilitate constant and active anammox reactions. In each experiment, 15 mL of the biomass suspension in media solution was filtered with filter paper  and differences in filter weights before and after filtration were used to calculate the suspended solid (S.S.) concentration after the filter had been oven-dried (at 105°C).2 gas to remove dissolved oxygen (DO). pH, DO, and the concentrations of NH4+ and NO2– were regularly measured to confirm the anammox activity of the biofilm, and pH (8.0) was maintained by adding KH2PO4 and Na2HPO4·12H2O solution. After the addition of NaNO2, (NH4)2SO4, and NaHCO3, we started the incubation and sampled 10 mL of media. Sampled media were filtered with a 0.20-μm syringe filter and then split into three; one for NO3– followed by the removal of NO2– (2– with high pH by the addition of 2M 2– andNaOH solution to prevent oxygen atom exchange between NO water (4+ with low pH by the addition of 4.8 M H2SO4 to prevent NH4+ from volatilizing. These subsamples were frozen (–30°C) until further analyses.The biofilm and incubation media solution  were sampled from the incubation membrane in the anammox reactor (SI Text 1.1). The incubation was performed anaerobically in the glovebox at room temperature (25–30°C) after the purging of media by N of NO2– , another2 purged) in the glovebox. Media consisted of NaHCO3 502 mg L–1; MgSO4·7H2O 603 mg L–1; CaCl2 180.5 mg L–1; KH2PO4 169 mg L–1; Na2HPO4·12H2O 282 mg L–1; trace elements of solution I  0.5 mL and solution II  0.5 mL. We added NaNO2 and (NH4)2SO4 to media (500 mL) with the anammox granules and then started the incubation at room temperature (25–30°C). We monitored pH (7.9 to 8.8) and NO2– to assess the progress of anammox. Sampling was performed as described in Experiment A.The granule biomass that accumulated at the bottom of the anammox reactor was sampled. Granules were rinsed anaerobically with new media (Nδ18O of water (δ18OH2O) was markedly higher (229‰) than that in Experiments A and B (–8‰). This “heavy” water was prepared by mixing 18O-labeled water (10% atom 18O) with Milli-Q water. During the incubation, media with biofilms were shaken at a constant temperature (30°C) and continuously purged with a gas mixture (95% Ar + 5% CO2) to maintain low DO levels. pH ranged between 7.1 and 7.5 and the monitoring and sampling scheme was identical to Experiment BWe incubated the biofilm collected from the incubation membrane in the anammox reactor with the same media used in Experiment B; however, the 4+ concentrations were measured during the incubation by the o-phthaldialdehyde (OPA) method    with USGS 32, 34, 35, and IAEA-2 as standards, and with the azide method  with TUAT-NO2-1 to TUAT-NO2-5  were evaluated using GC-IRMS with the denitrifier method after the conversion of NH4+ to NO3– by persulfate oxidation –1 and (R_SampleO/R_Oxygen)–1 where R_SampleN and R_SampleO are [15N/14N] and [18O/16O] of the sample, respectively, R_Nitrogen is [15N/14N] of atmospheric N2 and R_Oxygen is [18O/16O] of Vienna Standard Mean Ocean Water , residual NH4+ (δ15NNH4+_ANX), and the fraction of NH4+ reacting (NH4+f) in ANX reactor (15ΔAMX (The ammonium oxidation to N reactor  at a ste15ΔAMX = (δ15NNH4+_ANX – δ15NNH4+_NT) / NH4+f --- eq. (1)NH4+f = ([NH4+]NT – [NH4+]ANX) / [NH4+]NT4+]NT and [NH4+]ANX are the NH4+ concentrations in NT and ANX reactors, respectively.where ANX / ([NO2 – ]NT – [NO2–]ANX)b = ([NO3–]ANX – [NO3–]NT) / ([NO2–]NT – [NO2–]ANX)δ15NNO2–_NT is δ15NNO2– in NT reactor and the concentrations of NO2– and NO3– in NT and ANX reactors are [NO2–]NT, [NO2–]ANX, [NO3–]NT, and [NO3–]ANX, respectively.where The combination of eqs. (2) and (4) givesδ15NNO2–_NT = (1 – a – b) × δ15NN2_ANX + a × δ15NNO2–_ANX + b× δ15NNO3–_ANXa – b) × (δ15NNO2–_ANX – 15ΔAMXNIR) + a× δ15NNO2–_ANX + b × δ15NNO3–_ANX= (1 – δ15NNO2–_ANX – 15ΔAMXNIR – a × δ15NNO2–_ANX+ a × 15ΔAMXNIR – b × δ15NNO2–_ANX + b × 15ΔAMXNIR+ a × δ15NNO2–_ANX + b × δ15NNO3–_ANX= b × (δ15NNO3–_ANX – δ15NNO2–_ANX) + δ15NNO2–_ANX+ 15ΔAMXNIR × (a + b – 1)= b × 15ΔNXR) + δ15NNO2–_ANX + 15ΔAMXNIR × (a + b – 1)= – (15ΔAMXNIR = [δ15NNO2–_ANX – δ15NNO2–_NT – b × 15ΔNXR] / (a + b – 1) --- eq. (5)18O fractionation during nitrite oxidation to nitrate, we followed the approach described by 18EAMXcombined) because of the lack of detailed information on isotopic fractionation for the nitrite oxidation and oxygen atom incorporation during nitrite oxidation. Thus, we calculated 18EAMXcombined as follows:To calculate 18EAMXcombined = 2/3 δ18ONO2–_ANX + 1/3 δ18OH2O – δ18ONO3–_ANX--- eq. (6)δ18ONO2–_ANX, δ18OH2O, and δ18ONO3–_ANX are the 18O ratios of NO2–, water, and NO3– in ANX reactor, respectively.where 2– were then estimated from isotopic data.We developed an ordinary differential equation model as described by Fluxes regarding the anammox process  are defikAMO14N × [14NH4+] --- eq. (7)AMX = AMXNIR = x / (1 – x)) --- eq. (8)NXR = AMXNIR × (14N) fluxes of ammonium oxidation, nitrite oxidation, and reduction by anammox  .where AMX, NXR, and AMXNIR are the   in the a [NO2–])  and the 2–;Regarding NO14NO2–] = – NXR – AMXNIR --- eq. (9)d/dt [15NO2–] = – (R_NitriteN × NXR / 15εNXR)15εAMXNIR) --- eq. (10)– (R_NitriteN × AMXNIR / d/dt [16O2–] = – 2NXR – 2AMXNIR --- eq. (11)d/dt [N16O18O–] = – (R_NitriteO × 2NXR / 18εNXR)– (R_NitriteO × 2AMXNIR / 18εAMXNIR)– N16O18O–exch_OUT + N16O18O–exch_INd/dt [N18εNXR)– (R_NitriteO × 2AMXNIR / 18εAMXNIR)– kexch × [N16O18O–] + kexch×R_WaterO / 18εEQ--- eq. (12)= – , N16O18O–exch_OUT, and N16O18O–exch_IN  as described by 2– and H2O.where R_NitriteO, R_NitrateO, R_NitriteN, and R_NitrateN are the e and pH . We appl3–;Regarding NO14NO3–] = NXR --- eq. (13)d/dt [15NO3–] = (R_NitriteN × NXR / 15εNXR) --- eq. (14)d/dt [16O3–] = 3 NXR --- eq. (15)d/dt [N18O16O2–] = (R_NitriteO × 2 NXR / 18εNXR)+ (R_WaterO × NXR) / 18εH2ONXR) --- eq. (16)d/dt [N18εH2ONXR d/dt [15NH4+] = – (R_AmmoniumN × AMX/ 15εAMX) --- eq. (18)d/dt [15N / 14N of [NH4+] and 15εAMX is the N isotopic fractionation factor for NH4+ consumption by anammox (where R_AmmoniumN is the  anammox .2– and NH4+ to N2 and NO3– is as follows (The approximate stoichiometry of the anammox process converting NO2– + 1NH4+ → 1N2 + 0.3NO3– + 2H2O --- eq. (19)1.3NOx) together with kAMO14N with concentration data, which provided the AMX, AMXNIR, and NXR fluxes used in the calculation above . We assigned the range from 0 to 60‰  to estimate isotopic fractionation factors. We considered this 60‰ range for the curve-fitting estimate to be reasonable because isotopic fractionation factors larger than 60‰ are rarely observed  and consequently 18EAMXcombined , were not all successfully estimated for Experiments B and C. Based on these uncertainties in parameter estimations, we did not report these calculated values for Experiments B and C; however, we speculate that these calculated parameter sets support 18εAMXNIR as normal and 18εNXR being inverse isotope fractionation, as discussed below for Experiment A. The curve-fitting function (“multiple-fit” in BM software) (–6. BM codes for the anammox model for curve fittings with concentrations and isotopic data are provided in the Zenodo website (https://doi.org/10.5281/zenodo.3895346) and However, this stoichiometry between nitrite removal and nitrate production has been reported to vary d/dt [15NO2–] = – (R_NitriteN × NXR / 15εNXR)+ (R_NitrateN × NAR / 1518εNAR)– (R_NitriteN × DENNIR / 15εDENNIR)– (R_NitriteN × AMXNIR / 15εAMXNIR) --- eq. (21)d/dt [16O2–] = – 2 NXR + 2 NAR – 2 DENNIR – 2 AMXNIR --- eq. (22)d/dt [N1518εNAR + (R_NitrateO × 2 NAR / 1518εNAR) / 18εH2OBRNAR– (R_NitriteO × 2 DENNIR / 18εDENNIR)– (R_NitriteO × 2 AMXNIR / 18εAMXNIR) --- eq. (23a)d/dt [N18εH2OBRNAR is the 18O fractionation factor for the “branching effect”  + 1]d/dt  = NXR – NAR --- eq. (24)d/dt [15NO3–] = (R_NitriteN × NXR / 15εNXR) – (R_NitrateN × NAR / 1518εNAR) --- eq. (25)d/dt [18O16O2–] = 3 NXR – 3 NAR --- eq. (26)d/dt [N18O16O2–] = (R_NitriteO × 2 NXR / 18εNXR)+ (R_WaterO × NXR / 18εH2ONXR)– (R_NitrateO × 3 NAR / 1518εNAR) --- eq. (27)d/dt  and [NO2–] decreased during anammox (δ18ONO2– and δ18ONO3– did not change in Experiment A (δ18ONO3– increased by ~2‰ and δ18ONO2– decreased by ~3‰ in Experiment B (δ18O of H2O (229‰), δ18ONO2– and δ18ONO3– rapidly increased  for Kuenenia stuttgartiensis in batch incubation experiments  (Candidatus Jettenia” with the nirK gene ( 2 ± 2‰) . The simirK gene .15N and 18O fractionation factors during anaerobic nitrite oxidization to NO3– of –77.8‰ for 15εNXR and –20.6‰ for 18εNXR ; defined as  – (18ε / 15ε), where 18ε / 15ε is the ratio of isotopic fractionation for O and N during denitrification, respectively, and assigned as 1; see the inset in 2– was consumed. In the case of denitrification in which AMX / NAR is equal to 0 (indicating no anammox), δ18ONO3– vs δ15NNO3– was set to show a slope of 1 . To elucidate the relationship between Δ, AMX / NAR, and isotopic fractionation factors, we simulated the δ18ONO3– and δ15NNO3– trajectories along with the different AMX / NAR ratios and 15εAMXNXR ; however, Δ depended on AMX / NAR, 15εAMXNXR, and 15εNXR , our simulation exercise revealed that Δ, the offset from the 1:1 relationship between δ15N and δ18O, may be useful for detecting NXR (nitrite oxidation) in denitrifying systems in both freshwater and seawater.We developed an anammox-denitrification model with the estimated isotopic fractionation factors  denitrification with auxiliary Nap NO3– reductase may exhibit a 2:1 rather than 1:1 relationship between δ15N and δ18O, resulting in an offset from the 1:1 relationship  is not considered to be a major environmental sink for NO3–  may induce an offset from the denitrification trajectory . In practice, Δ may be evaluated with time-course samplings or short incubation studies to investigate the occurrence of anammox, similar to denitrification. This technique will be advantageous because of its potential in evaluations of the quantitative contribution in situ of anammox versus denitrification. Although the detection and quantification of functional genes in denitrification and anammox may be readily performed, difficulties are associated with detecting the in situ occurrence of denitrification and anammox. Although the isotopic fractionation factors used also need to be considered, Δ is a promising parameter to complement molecular data and the results from laboratory incubation experiments in the study of anammox.We estimated Microbes Environ 35: ME20031.Kotajima, S., Koba, K., Ikeda, D., Terada, A., Isaka, K., Nishina, K., et al. (2020) Nitrogen and Oxygen Isotope Signatures of Nitrogen Compounds during Anammox in the Laboratory and a Wastewater Treatment Plant. https://doi.org/10.1264/jsme2.ME20031Supplementary Material