Synthesis of New Ruthenium（Ⅱ）Bipyridyl Complexes and Studies on Their Photophysical and Photoelectrochemical Properties

Two new mixed-ligand ruthenium(Ⅱ） complexes,Ru(dcbpy)-(LL)NCS)2[where dcbpy=4,4‘-dicarboxyl-2,2‘‘-bipyridine,LL=4,4‘-bis(N-methyl-anilinomethyl)-2,2‘‘-bipyridine(2)],were synthesized,and the tphotophysical properties of these complexes were studied.The metal-to-ligand charge transfer (MLCT) transitions of these complexes exhibited solvatochromic effect due to the existence of NCS ligands.The MLCT energies also strongly depend on the pH values of the solutions because of protonation and deprotonation of the carboxyl groups.The pKa values of the ground state,4.0 for 1 and 3.8 for 2,were obtained from the titration curves.The photoelectrochemical properties of 1 and 2 as sensitizers in sandwich-type solar cells have been studied.Complex 1 exhibited better photoelectrochemical behavior than complex 2 as expected.It was proved that the design of mixed-ligand complex by introducing electron donating group in one of the ligands should be a promising approach.     

Synthesis,characterization,structures and magnetic property of chiral oxalate-bridged dicopper(Ⅱ) complexes

The oxalato-bridged dicopper(II) complexes [Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2] (1),[Cu2(μ-ox)(LRR)2(CH3COCH3)2(ClO4)2](1a),[Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2] (2) and [Cu2(μ-ox)(LRR)(LSS)2(CH3COCH3)2(ClO4)2] (3) [LRR = (8R,10R)-(-)-[4,5]-pineno2,2′-bipyridine,LSS = (8S,10S)-(+)-[4,5]-pineno-2,2′-bipyridine;ox2= oxalate] were first prepared.A possible mechanism for the formation of the chial dicopper(II) complexes was proposed.Based on elemental analysis,conductance measurement,UV-Vis spectra,CD spectra and X-ray single-crystal diffraction,the oxalato-bridged structures of 1 and 2 were deduced to adopt two Cu(II) ions and the bridged oxalate lying in the nearly same plane.The crystal structures of 1a and 3 reveal that the coordination geometry around each Cu(II) ion is an elongated and distorted octahedron and two axial solvent molecules and two perchlorate ions are anti to each other respectively in both binuclear molecules.The solution CD spectra of 1 and 2 in the visible d-d range show very weak Cotton effects with peaks at 588 and 779 nm,which are approximately of mirror image,suggesting the optical activities may be derived from the vicinal effects of the chiragenic centers at the pinene group of LRR and LSS,respectively.Complex 1 has been characterized by variable-temperature magnetic susceptibility and the data was least-square fitted to the Blenaey-Bowers equation.The exchange integral J was found to be -338.41(4) cm-1,indicating a strong antiferromagnetic interaction between two copper(II) ions.     

New Copper（Ⅱ） and Nickel（Ⅱ） Complexes of 4-Morpholinoacetophenone Thiosemicarbazone： Structural, Electrochemical and Antimicrobial Studies

4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel（Ⅱ） and copper（Ⅱ） complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods （FT-IR, ^1H NMR） and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu（MAPT）2]Cl2 complex shows Cu（Ⅱ）/Cu（Ⅰ） couple and quasi-reversible wave associated with the Cu（Ⅲ）/Cu（Ⅱ） process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis.     

Hydrothermal Synthesis and Structural Characterization of a Novel Organic—Inorganic Hybrid Compound {[Cu（2,2′—bpy）2]2—Mo8O26}

A novel organic-inorganic hybrid compound {[Cu(2,2′-bpy)2]2Mo8O26} has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group, Pna21,with a=2.4164(5),b=1.8281(4),c=1.1877(2)nm,V=5.247(2)nm^3,Z=4,and final R1=0.0331,wR2=0.0727.The structure consists of discrete {[Cu(2,2′-bpy)2]2Mo8O26} clusters,constructed from a β-octamolybdate subunit[Mo8O26]^4- covalently bonded to two [Cu(2,2′-bpy)2]^2 coordination complex cations via bridging oxo groups.In addition,the spectroscopic properties and thernal behavior of this compound have been investigated by spectroscopic techniques (UV-vis,IR,Raman and EPR spectra) and TG analysis.     

Hybrid Tungstocuprate [Cu(2,2′-bpy)_3]_2H_4[CuW_(12)O_(40)]·6H_2O Based on Keggin Polyoxoanion [CuW_(12)O_(40)]~(6-) with Cu~Ⅱas Heteroatom

A novel hybrid tungstocuprate(Ⅱ) [Cu(2,2′-bpy)3]2H4[CuW12O40]·6H2O(2,2′-bpy=2,2′-bipyridine) was synthesized via hydrothermal method and characterized using elemental analyses, IR, UV, XPS, TG-DSC, EPR, and X-ray single crystal diffraction. The structural analysis shows that the complex consists of an unusual Keggin-type polyoxoanion [CuW12O40]6- and a pair of chiral complex cations [Cu(2,2′-bpy)3] together with four protons and six crystallization water molecules, and the Keggin polyoxoanion is connected with [Cu(2,2′-bpy)3] via multiple C—H…O hydrogen bonds resulting in a dimer.     

Synthesis,Structure and Characterization of [Cu(2,2′-bpy)_2][{Cu(2,2′-bpy)_2}_2W_(12)O_(40)(H_2)]·4H_2O

An organic-inorganic compound [Cu(2,2′-bpy)2][{Cu(2,2′-bpy)2}2W12O40(H2)]·4H2O (Mr = 4048.00) was prepared from the hydrothermal reaction of Na2WO4·2H2O, CuCl2·2H2O, 2,2′-bipyridine (2,2′-bpy) and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196(8), b = 20.4212(8), c = 21.8129(9) , β = 96.992(3)°, V = 8365.0(6) 3, Dc = 3.214 g/cm3, Z = 4, μ(MoKα) = 17.269 mm-1 and F(000) = 7324. Of the 119837 total reflections, 17315 were unique (Rint = 0.0489). The final R = 0.0385 and wR = 0.0770 for 11142 observed reflections with I > 2σ(I). Single-crystal X-ray diffraction reveals that the structure is composed of [{Cu(2,2′-bpy)2}2W12O40(H2)]2- anions, discrete [Cu(2,2′-bpy)2]2+ cations and lattice water molecules, and the anion is made up of a {W12O40(H2)}6- α-Keggin core decorated with two {Cu(2,2′-bpy)2}2+ groups through bridging oxygen atoms.     

Theoretical Studies on the Cu-Cu Interaction and Stability of [Cu_a(Ph_2Ppy)_b(CH_3CN)_c]~(a+) (a=1～2,b=1～3,c=0～2)

To study the Cu-Cu interaction and stability of the title complexes,the structures of complexes [Cu(Ph2Ppy)(CH3CN)]+ 1,[Cu(Ph2Ppy)]+ 2,[Cu2(Ph2Ppy)2(CH3CN)2]2+ 3,[Cu2(Ph2Ppy)2(CH3CN)]2+ 4,[Cu2(Ph2Ppy)2]2+ 5 and [Cu2(Ph2Ppy)3(CH3CN)]2+ 6 were calculated by density functional theory PBE0 method,and the following conclusions can be drawn:(1) There is no orbital overlapping between two Cu atoms,indicating no Cu-Cu orbital interaction exists in complexes 3～6.Due to a breakdown of the closed shell configuration of Cu atoms,the weak Cu-Cu interactions result from the 3dCu → 4sCu' charge-transfer in 4～6.The Cu-Cu interaction strength follows 5 6 4,implying that there are stronger Cu-Cu interactions in the complexes with fewer CH3CN or more Ph2Ppy ligands.(2) The calculated interaction energies suggest that the coordination of Cu to Ph2Ppy is stronger than that to CH3CN.In 3～6,there are weaker interactions between Cu and CH3CN or Ph2Ppy in the complexes with more CH3CN or Ph2Ppy ligands.(3) The P-Cu and N-Cu interactions are much stronger than the Cu-Cu interaction,so we mainly attribute the stabilities of the binuclear complexes to the eight-membered rings Cu2P2N2C2.     

Cobalt(Ⅱ) and Cadimium(Ⅱ) Metal-organic Frameworks Supported by a Multicarboxylate Ligand

Two metal-organic frameworks(MOFs) of formulae [Co_7(L)_3(4,4?-BPy)_2(OH)_2(H_2O)_6]·-4 H_2O(1) and [Cd_2(L)(2,2?-BPy)2]n(2, H_4L = 5-(3,5-dicarboxybenzyloxy)-isophthalic acid,2,2?-BPy = 2,2?-bipyridine, 4,4?-BPy = 4,4?-bipyridine) were synthesized under solvothermal conditions. The structures of 1 and 2 were characterized by X-ray single-crystal diffraction analysis.In complex 1, six cobalt atoms were connected by oxygen atoms to form a defect dicubane structure. The defect dicubane structures were further linked by Co(4,4?-BPy) units to generate a3-D network structure. Compound 2 displays a 2-D chain structure. The photoluminescent property of complex 2 is investigated. The results show the exclusive luminescence emission bands being originated from intraligand π-π* transitions.     

PREPARATION AND MAGNETIC PROPERTIES OF POLY(SCHIFF BASE) COMPLEXES CONTAINING PHENANTHROLINE UNITS

Two poly(Schiff base)s (PDBT and PDPE) were synthesized by polycondensation of 1,10-phenanthroline-5,6- dione (PD) with 2,2′-diamino-4,4′-bithiazole (DABT) and 4,4′-diaminodiphenyl ether (DAPE),respectively.The structures of the polymers were determined by FTIR and element analysis.The metal (Fe~(2+),Ni~(2+)) complexes were prepared from the polymers with FeSO_4 or NiSO_4,and the metal contents of the complexes were measured by complexometric titration.The magnetic behaviors of the complexes were examine...     

Synthesis, Crystal Structure and Thermal Stability of a Nickel（Ⅱ） Complex with Bicycle[2.2.1]-2-hepten-5,6-dicarboxylic Acid

The nickel complex {Ni(2,2-bipy)(H2O)3[C8H11O2(COO)]}(H2O)3 with bicycle-[2.2.1]-2-hepten-5,6-dicarboxylic acid [C7H8(COOH)2] and 2,2'-bipyridine (bipy) as ligands has been synthesized and characterized. It crystallizes in monoclinic, space group P , with a = 0.74975(3), b = 1.20309(4), c = 1.30593(4) nm, α = 109.861(2), β = 98.519(2), γ = 90.575(2)o, V = 1.09337(7) nm3, Dc = 1.552 g/cm3, Z = 2, F(000) = 524, the final GOOF = 1.064, R = 0.0397 and wR = 0.1171. The crystal structure shows that the nickel ion is coordinated with four oxygen atoms from one bicycle[2.2.1]-2-hepten-5,6-dicarboxylic acid molecule and three water molecules and two nitrogen atoms from the 2,2′-bipyridine molecule, forming a distorted octahedral coordination geometry. The result of TG analysis shows that the title complex is stable under 200.0 ℃.     

Dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylate and bis(dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylato‐κ2N,N′)copper(I) tetrafluoroborate

The single‐crystal X‐ray structures of dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylate, C₁₄H₁₂N₂O₄, and the copper(I) coordination complex bis(dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylato‐κ²N,N′)copper(I) tetrafluoroborate, [Cu(C₁₄H₁₂N₂O₄)₂]BF₄, are reported. The uncoordinated ligand crystallizes across an inversion centre and adopts the anticipated anti pyridyl arrangement with coplanar pyridyl rings. In contrast, upon coordination of copper(I), the ligand adopts an arrangement of pyridyl donors facilitating chelating metal coordination and an increased inter‐pyridyl twisting within each ligand. The distortion of each ligand contrasts with comparable copper(I) complexes of unfunctionalized 2,2′‐bipyridine.     

Syntheses,Crystal Structures and Cytotoxities of Silver (I) Complexes of 2,2′‐Bipyridines and 1,10‐Phenanthroline

The syntheses, characterizations and in vitro cytotoxities of seven soluble silver (I) compounds (1–7) with 2,2′‐bipyridine (bpy), 5,5′‐dimethyl‐2,2′‐bipyridine (dmbpy) and 1, 10‐phenanthroline (phen) are described. Two of the complexes, [Ag(dmbpy)(NO₃)] (1) and [Ag(dmbpy)]ClO₄(2), have been structurally established by single‐crystal X‐ray diffraction, which reveals the silver(I) atom in compound 1 is in a Y‐shape coordination geometry with two N atoms (av. Ag? N = 227.8 pm) from a chelate dmbpy ligand and an O atom (Ag? O=221.8(4) pm) from a monodentate nitrate. The Ag(I) atom in compound 2 is three‐coordinated by three N atoms, two of which are from a chelate dmbpy, and one from an acetonitrile ligand. The seven compounds showed strong cytotoxities in vitro to both normal and carcinoma cells.     

Synthesis and photophysical properties of novel amphiphilic ruthenium (II) complexes containing 4,4′‐dialkylaminomethyl‐2,2′‐bipyridyl ligands

The synthesis of a number of new 2,2′‐bipyridine ligands functionalized with bulky amino side groups is reported. Three homoleptic polypyridyl ruthenium (II) complexes, [Ru(L)₃]²⁺ 2(PF₆^?), where L is 4,4′‐dioctylaminomethyl‐2,2′‐bipyridine (Ru4a), 4,4′‐didodecylaminomethyl‐2,2′‐bipyridine (Ru4b) and 4,4′‐dioctadodecylaminomethyl‐2,2′‐bipyridine (Ru4c), have been synthesized. These compounds were characterized and their photophysical properties examined. The electronic spectra of three complexes show pyridyl π → π* transitions in the UV region and metal‐to‐ligand charge transfer bands in the visible region. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis and Structure of New Trimethylplatinum(IV) Iodide Complexes of 2,2′‐Bipyridine Ligands

The synthesis and structural characterization of four new trimethylplatinum(IV) iodide complexes of 2,2′‐bipyridine ligands {[PtMe₃(4,4′‐Clbipy)I] ( 1 ), [PtMe₃(4,4′‐Brbipy)I] ( 2 ), [PtMe₃(4,4′‐CNbipy)I] ( 3 ) and [PtMe₃(4,4′‐NO₂bipy)I] ( 4 )} are reported. The ¹H NMR spectra of the complexes reveal the presence of two chemically distinct methyl groups in the complexes. X‐ray crystal structures of complexes 1 – 4 show that the platinum metal center in each of the complexes form distorted octahedral structure being surrounded by methyl groups, bipyridine ligand, and iodine atom. Furthermore, the crystal packing study shows that self‐assembly of the complexes are governed by weak hydrogen bonding and other non‐covalent interactions such as π ··· π, halogen ··· π and C–H ··· π interactions. Complex 1 exhibits infinite one‐dimensional zigzag chain structure and other three complexes form infinite ladder type structures.     

Four novel lanthanide complexes with 4‐ethylbenzoic acid and 5,5′‐dimethy‐2,2′‐bipyridine: Structures,luminescent, thermal properties and bacteriostatic activities

Four new lanthanide complexes [Ln(4‐EBA)₃(5,5′‐DM‐2,2′‐bipy)]₂·2C₂H₅OH (Ln = Ho ( 1 ), Tb ( 2 ), Er ( 3 )); [Ln(4‐EBA)₃(4‐EBAH)(5,5′‐DM‐2,2′‐bipy)]₂ (Ln = Eu( 4 ); 4‐EBA =4‐ethylbenzoate; 5,5′‐DM‐2,2′‐bipy =5,5′‐dimethy‐2,2′‐bipyridine; 4‐EBAH = 4‐ethylbenzoic acid) have been synthesized and characterized by elemental analysis and IR spectra. The single crystal results reveal that complexes 1 – 3 are isostructural. It is worth noting that the mole ratios of the carboxylate ligands and neutral ligands is 4:1 in complex 4 , which is different from the former and has been rarely reported. Nevertheless, all complexes are connected to form 1D chain by π ···π wake staking interactions. Additionally, the complexes 2 (Tb(III)) and 4 (Eu(III)) exhibit characteristic luminescent properties, indicating that ligands can be used as sensitizing chromophore in these systems. The thermal decomposition mechanism of the complexes has been investigated by TG/DSC–FTIR technology. Stacked plots of the FTIR spectra of the evolved gases show complexes broken down into H₂O, CO₂, and other gaseous molecules as well as the gaseous organic fragments. The studies on bacteriostatic activities of complexes show that four complexes have good bacteriostatic activities against Candida albicans but no bacteriostatic activity on Escherichia coli , and Staphylococcus aureus . Additionally, the complexes 1 to 3 have better bacteriostatic activities on Candida albicans than complex 4 .     

Construction of three types of lanthanide complexes based on 3,4‐dimethylbenzoic acid and 5,5′‐dimethyl‐2,2′‐bipyridine: Syntheses,Structures, Thermodynamic properties,Luminescence, and Bacteriostatic activities

Three novel lanthanide complexes [Er (3,4‐DMBA)₃(5,5′‐DM‐2,2′‐bipy)(H₂O)] ( 1 ); [Tb₂ (3,4‐DMBA)₆(5,5′‐DM‐2,2′‐bipy)₂(H₂O)] ( 2 ); [Eu (3,4‐DMBA)₃(3,4‐DMHBA)(5,5′‐DM‐2,2′‐bipy)]₂ ( 3 ) (3,4‐DMHBA = 3,4‐dimethylbenzoic acid, 5,5′‐DM‐2,2′‐bipy =5,5′‐dimethyl‐2,2′‐bipyridine) were successfully synthesized via conventional solution method at room temperature and structurally characterized by single crystal diffraction. The structures of the complexes 1 – 3 were confirmed on the basis of elemental analysis, coordination titration analysis, IR and XRD. The molecular structures of complexes 2 and 3 are very particular: complex 2 has two same central metal ions but each metal ion has different coordination environment; in structure of the complex 3 , there are eight carboxylic acid ligands coordinated to the central metal ions, which have rarely been reported previously. The thermal decomposition mechanism of complexes 1 – 3 were investigated by the technology of simultaneous TG/DSC‐FTIR. The heat capacities of the complexes were recorded by means of DSC over the range of from 253.15 K to 345.15 K. The thermodynamic parameters, the smoothed values of heat capacities, enthalpy (H_T‐H_298.15K) and entropy (S_T‐S_298.15K) were also calculated. The bacteriostatic activities of the complexes were evaluated against Staphylococcus aureus, Escherichia coli and Candida albicans. What's more, the luminescence properties of complexes 2 and 3 were discussed, and their fluorescence lifetimes as well as the quantum yield of the Eu (III) were measured. To elucidate the energy transfer process of complexes 2 and 3, the energy levels of the relevant electronic states have been estimated.     

Effect of Metal Ions on the Structures of Coordination Polymers Based on Biphenyl‐2,2′,4,4′‐Tetracarboxylate

Two new coordination polymers, {[Cd₂(btc)(2,2′‐bpy)₂] · H₂O}_n ( 1 ) and [Zn₂(btc)(2,2′‐bpy)(H₂O)]_n ( 2 ) (H₄btc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine), were synthesized hydrothermally under similar conditions and characterized by elemental analysis, IR spectra, TGA, and single‐crystal X‐ray diffraction analysis. In complexes 1 and 2 , the (btc)^4– ligand acts as connectors to link metal ions to give a 2D bilayer network of 1 and a 3D metal‐organic framework of 2 , respectively. The differences in the structures are induced by diverging coordination modes of the (btc)^4– ligand, which can be attributed to the difference metal ions in sizes. The results indicate that metal ions have significant effects on the formation and structures of the final complexes. Additionally, the fluorescent properties of the two complexes were also studied in the solid state at room temperature.     

Metallomacrocycles with a Difference: Macrocyclic Complexes with Exocyclic Ruthenium(II)‐Containing Domains

The templated synthesis of organic macrocycles containing rings of up to 96 atoms and three 2,2′‐bipyridine (bpy) units is described. Starting with the bpy‐centred ligands 5,5′‐bis[3‐(1,4‐dioxahept‐6‐enylphenyl)]‐2,2′‐bipyridine and 5,5′‐bis[3‐(1,4,7‐trioxadec‐9‐enylphenyl)]‐2,2′‐bipyridine, we have applied Grubbs’ methodology to couple the terminal alkene units of the coordinated ligands in [FeL₃]²⁺ complexes. Hydrogenation and demetallation of the iron(II)‐containing macrocyclic complexes results in the isolation of large organic macrocycles. The latter bind {Ru(bpy)₂} units to give macrocyclic complexes with exocyclic ruthenium(II)‐containing domains. The complex [Ru(bpy)₂(L)]²⁺ (isolated as the hexafluorophosphate salt), in which L=5,5′‐bis[3‐(1,4,7,10‐tetraoxatridec‐12‐enylphenyl)]‐2,2′‐bipyridine, undergoes intramolecular ring‐closing metathesis to yield a macrocycle which retains the exocyclic {Ru(bpy)₂} unit. The poly(ethyleneoxy) domains in the latter macrocycle readily scavenge sodium ions, as proven by single‐crystal X‐ray diffraction and atomic absorption spectroscopy data for the bulk sample. In addition to the new compounds, a series of model complexes have been fully characterized, and representative single‐crystal X‐ray structural data are presented for iron(II) and ruthenium(II) acyclic and macrocyclic species.     

Synthesis and Characterization of Monomeric Aryloxo Palladium Complexes of the Type [Pd(N–N)(OAr)(C6F5)]. Crystal Structure of [Pd(tmeda)(C6F5)(OC6H4NO2‐p)]

Mononuclear palladium‐hydroxo complexes of the type [Pd(N–N)(C₆F₅)(OH)][(N–N) = 2,2′‐bipyridine (bipy), 4,4′‐dimethyl‐2,2′‐bipyridine (Me₂bipy), 1,10‐phenantroline (phen) or N,N,N′,N′‐tetramethylethylenediamine (tmeda) react with phenols ArOH in tetrahydrofuran giving the corresponding aryloxo complexes [Pd(N–N)(C₆F₅)(OAr)]. Elemental analyses and spectroscopic (IR, ¹H and ¹⁹F) methods have been used to characterize the new complexes. The X‐ray crystal structure of [Pd(tmeda)(C₆F₅)(OC₆H₄NO₂‐p)] has been determined. In the crystal packing the planes defined by two C₆H₄ rings show a parallel orientation. There are also intermolecular C–H···F and C‐H···O hydrogen bonds.     

Chlorido(dimethyl 2,2′‐bipyridine‐4,4′‐dicarboxylate‐κ2N,N′)(η5‐pentamethylcyclopentadienyl)rhodium(III) chloride 1‐hydroxypyrrolidine‐2,5‐dione disolvate

The title complex, [Rh(C₁₀H₁₅)Cl(C₁₄H₁₂N₂O₄)]Cl·2C₄H₅NO₃, has been synthesized by a substitution reaction of the precursor [bis(2,5‐dioxopyrrolidin‐1‐yl) 2,2′‐bipyridine‐4,4′‐dicarboxylate]chlorido(pentamethylcyclopentadienyl)rhodium(III) chloride with NaOCH₃. The Rh^III cation is located in an RhC₅N₂Cl eight‐coordinated environment. In the crystal, 1‐hydroxypyrrolidine‐2,5‐dione (NHS) solvent molecules form strong hydrogen bonds with the Cl⁻ counter‐anions in the lattice and weak hydrogen bonds with the pentamethylcyclopentadienyl (Cp*) ligands. Hydrogen bonding between the Cp* ligands, the NHS solvent molecules and the Cl⁻ counter‐anions form links in a V‐shaped chain of Rh^III complex cations along the c axis. Weak hydrogen bonds between the dimethyl 2,2′‐bipyridine‐4,4′‐dicarboxylate ligands and the Cl⁻ counter‐anions connect the components into a supramolecular three‐dimensional network. The synthetic route to the dimethyl 2,2′‐bipyridine‐4,4′‐dicarboxylate‐containing rhodium complex from the [bis(2,5‐dioxopyrrolidin‐1‐yl) 2,2′‐bipyridine‐4,4′‐dicarboxylate]rhodium(III) precursor may be applied to link Rh catalysts to the surface of electrodes.