Effects of Different Amount of Crystalline Solvate Molecules on Solid Structures and Photophysical Properties of a Platinum(II) Moiety with 4,4′‐Dibromo‐2,2′‐Bipyridine Ligand

A platinum(II) complex Pt(DiBrbpy)Cl₂ ( 1 ) based on 4,4′‐dibromo‐2,2′‐bipyridine ligand was synthesized and characterized. Interestingly, two solvated phases of 1 with different amounts of crystalline CH₂Cl₂ molecules, 1· 1/3(CH₂Cl₂) (yellow) and 1· 3/2(CH₂Cl₂) (red), were obtained. In the solid state, 1· 1/3(CH₂Cl₂) exhibits a 3D supramolecular structure based on Pt(DiBrbpy)Cl₂ monomer and emits a weak yellow luminescence at 541 nm (579, sh). In contrast, 1· 3/2(CH₂Cl₂) displays a 2D layer structure based on Pt(DiBrbpy)Cl₂ dimeric units and has a strong red luminescence centered at 624 nm. The results show that crystalline solvate molecule amount can not only influence the packing structures but also photophysical properties of the platinum moiety in solid state. Furthermore, the absorption and luminescence spectra of both phases were studied by TD‐DFT calculations.     

Synthesis and Characterization of Heteroleptic Ru(II) Complexes Based on 4,4′‐Bis((E)‐styryl)‐2,2′‐bipyridine as Ancillary Ligand and Application for Dye‐Sensitized Solar Cells

Heteroleptic Ru(II) complexes were designed based on 4,4′‐bis((E)‐styryl)‐2,2′‐bipyridine (bsbpy) as an ancillary ligand for dye‐sensitized solar cells (DSSCs), and those Ru(II) sensitizers, [Ru(L)(bsbpy)(NCS)₂][TBA] (TBA; tetrabutylammonium), were synthesized according to a typical one‐pot reaction of [RuCl₂(p‐cymene)]₂ with the corresponding anchoring ligands (where L = 4,4′‐dicarboxy‐2,2′‐bipyridine (dcbpy), 4,4′‐bis((E)‐carboxyvinyl)‐2,2′‐bipyridine (dcvbpy), 4,7‐dicarboxy‐1,10‐phenanthroline (dcphen), or 4,7‐bis((E)‐carboxyvinyl)‐1,10‐phenanthroline (dcvphen)). The new Ru(II) dyes, [Ru(L)(bsbpy)(NCS)₂][TBA] that incorporated vinyl spacer(s) into ancillary and/or anchoring ligand displayed red‐shifted bands over the overall UV/VIS region relative to the absorption spectra of N719 . A combination of bsbpy ancillary and dcphen anchoring ligand showed the best result for the overall power conversion efficiency (η); i.e., a DSSC fabricated with [Ru(dcphen)(bsbpy)(NCS)₂][TBA] exhibited a power conversion efficiency (η) of 2.98% (compare to N719 , 4.82%).     

Bipyridine‐Modulated Palladium‐Catalyzed Oxidative Heck‐Type Reactions of Arylboronic Acids with Olefins

We have demonstrated that 4,4′‐dimethyl 2,2′‐bipyridine as ligand for Pd(II) catalysts was very efficient for oxidative Heck‐type coupling reaction of arylboronic acids with olefins in DMA or CH₃CN under atm air at 80 °C. The presence of chelated bipyridine ligand isindispensable to achieve high reaction yields and to suppress the formation of biphenyl as homocoupled byproduct.     

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.     

Dichloro­(4,4′‐dialkyl‐2,2′‐bipyridine‐κ2N,N′)platinum(II), where alkyl is pentyl and heptyl

Dichloro­(4,4′‐dipentyl‐2,2′‐bipyridine‐κ²N,N′)platinum(II), [PtCl₂(C₂₀H₂₈N₂)], adopts a discrete π–π stacking structure, where the alkyl chains are located in a random manner. In contrast, dichloro­(4,4′‐diheptyl‐2,2′‐bipyridine‐κ²N,N′)platinum(II), [PtCl₂(C₂₄H₃₆N₂)], forms a layer structure comprised of alkyl chain layers and paired coordination sites, as observed for analogous complexes with longer alkyl chains.     

Synthesis of Amphiphilic RuII Heteroleptic Complexes Based on Benzo[1,2‐b:4,5‐b′]dithiophene: Relevance of the Half‐Sandwich Complex Intermediate and Solvent Compatibility

The detailed synthesis and characterization of four ruthenium(II) complexes [RuLL′(NCS)₂] is reported, in which L represents a 2,2′‐bipyridine ligand functionalized at the 4,4′ positions with benzo[1,2‐b:4,5‐b′]dithiophene derivatives (BDT) and L′ is 2,2′‐bipyridine‐4,4′‐dicarboxylic acid unit (dcbpy) (NCS=isothiocyanate). The reaction conditions were adapted and optimized for the preparation of these amphiphilic complexes with a strong lipophilic character. The photovoltaic performances of these complexes were tested in TiO₂ dye‐sensitized solar cell (DSSC) achieving efficiencies in the range of 3–4.5 % under simulated one sun illumination (AM1.5G).     

Syntheses and crystal structures of triorganotin (IV) derivatives with 2,2′‐bipyridine‐4,4′‐dicarboxylic acid

Four organotin complexes with 2,2′‐bipyridine‐4,4′‐dicarboxylic acid, H₂dcbp: (Ph₃n)₂(dcbp) 1 , [(PhCH₂)₃n]₂(dcbp) ⋅ 2CH₃OH 2 , [(Me₃Sn)₂(dcbp)]_n 3 , [(Bu₃Sn)₂(dcbp)]_n 4 have been synthesized. The complexes 1–4 were characterized by elemental, IR, ¹H, ¹³C, ¹¹⁹n NMR, and X‐ray crystallographic analyses. Crystal structures show that complex 1 is a monomer with one ligand coordinated to two triorganotin moieties, and a 1D infinite polymeric chain generates via intermolecular C H⋅⋅⋅N hydrogen bond; complex 2 is also a monomer and forms a 2D network by intermolecular O–H⋅⋅⋅O weak interaction; both of complexes 3 and 4 form 2D network structures where 2,2′‐bipyridine‐4,4′‐dicarboxylate acts as a tetradentate ligand coordinated to trimethyltin and tri‐n‐butyltin ions, respectively. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:19–28, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20506     

Hydrothermal Syntheses and Crystal Structures of Two Layered Nickel(II) Coordination Polymers Based on 1,2,3‐Benzenetricarboxylic Acid

The hydrothermal reactions of Ni(II), 1,2,3‐benzenetricarboxylic acid (1,2,3‐H₃btc) and 4,4′‐bipyridine (4,4′‐bpy)/1,2‐bis(4‐pyridyl)ethane (bpa) yield two layered nickel(II) coordination polymers, [Ni₂(1,2,3‐btc)(OAc)‐(4,4′‐bpy)₂(H₂O)]·2H₂O ( 1 ) and [Ni(ip)(bpa)] ( 2 ) (ip=isophthalate), respectively. Both complexes are 2‐D coordination network based on 1‐D Ni‐carboxylate chains. The 1,2,3‐btc ligand adopts 3‐bridging mode in complex 1 , but transformed to isophthalate (ip) ligand through decarboxylation in 2 . The formation of the two complexes indicates that hydrothermal conditions andin‐situ ligand reaction have significant effect on constructing coordination polymers.     

(4,4′‐Bipyridine)mercury(II) Coordination Polymers,Syntheses, and Structures

Mercury(II) complexes with 4,4′‐bipyridine (4,4′‐bipy) ligand were synthesized and characterized by elemental analysis, and IR, ¹H‐ and ¹³C‐NMR spectroscopy. The structures of the complexes [Hg₃(4,4′‐bipy)₂(CH₃COO)₂(SCN)₄]_n ( 1 ), [Hg₅(4,4′‐bipy)₅(SCN)₁₀]_n ( 2 ), [Hg₂(4,4′‐bipy)₂(CH₃COO)₂]_n(ClO₄)_2n ( 3 ), and [Hg(4,4′‐bipy)I₂]_n ( 4 ) were determined by X‐ray crystallography. The single‐crystal X‐ray data show that 2 and 4 are one‐dimensional zigzag polymers with four‐coordinate Hg‐atoms, whereas 1 is a one‐dimensional helical chain with two four‐coordinate and one six‐coordinate Hg‐atom. Complex 3 is a two‐dimensional polymer with a five‐coordinate Hg‐atom. These results show the capacity of the Hg‐ion to act as a soft acid that is capable to form compounds with coordination numbers four, five, and six and consequently to produce different forms of coordination polymers, containing one‐ and two‐dimensional networks.     

DNA interaction and cleavage studies of ancillary chiral ligand and N,N‐donor ligands coordinated platinum(II) complexes

Four new platinum(II) complexes [Pt(dpen)(bpy)](ClO₄)₂ ( 1 ) , [Pt(dpen)(phen)](ClO₄)₂ ( 2 ), [Pt(dpen)(dpq)](ClO₄)₂ ( 3 ) and [Pt(dpen)(dppz)](ClO₄)₂ ( 4 ) comprising of different N,N‐donor ligands, viz., 2,2′‐bipyridine (bpy), 1,l0‐phenanthroline (phen), dipyridoquinoxaline (dpq), dipyrido‐[3,2‐d:2¢,3¢‐f –phenazine] (dppz), and chiral ancillary ligand 1R,2R ‐1,2‐diphenylethylenediamine (dpen) have been synthesized and characterized. The interaction of these complexes 1–4 with calf‐thymus DNA (CT‐DNA) has been explored using absorption, circular dichroism spectral and cyclic voltammetric studies. The absorption spectrum of complex 4 with dppz ligand exhibits a major red shift with an overall hypochromic as well as a hyperchromic effect in the presence of DNA, other complexes ( 1 – 3 ) show only hypochromism. From these absorption spectral studies, the intercalative ability of the complexes follows the order as, 4  >  3  >  2  >  1 , which is further confirmed by CD and cyclic voltammetry measurements. CD spectral studies show that DNA becomes more A ‐like upon interaction with the complexes 1 & 2 but the complexes 3 & 4 bring about B ‐form to Z ‐ form DNA conformational transition. The DNA cleavage study of these Pt(II) complexes 1–4 carried out by gel electrophoresis revealed that complexes 1–4 can cleave super coiled (SC) pUC18 DNA efficiently into open circular form (form II) under hydrolytic and oxidative conditions.     

Oxidative addition of 1,4‐dichloro‐2‐butyne to an organoplatinum complex: A new precursor for synthesis of ultrasmall Pt nanoparticles thin film at liquid/liquid interface as the electrocatalyst in methanol oxidation reaction

In this study, the usage of ClCH₂CCCH₂Cl alkyne as a reagent for the oxidative addition reaction with organoplatinum?(II) complex [PtMe₂(bipy)] ( 1 ), in which bipy = 2,2′‐bipyridine to give a mixture including of trans‐[PtClMe₂(CH₂CCCH₂Cl)(bipy)] ( 2a ) and a cis‐[PtClMe₂(CH₂CCCH₂Cl)(bipy)] ( 2b ) complexes is reported. Kinetic study was investigated by monitoring the disappearance of the metal‐to‐ligand charge transfer (MLCT) band in the UV–Vis spectra. ¹H NMR experimental results confirmed that trans isomer ( 2a ) is more stable than its corresponding cis isomer. A liquid–liquid planar interface has been employed as a template for self‐assembly of platinum nanoparticles. The as prepared complex was applied for the synthesis of platinum thin film that characterized by transmission electron microscopy (TEM), X‐ray diffraction (XRD), energy dispersive analysis of X‐rays (EDAX), field emission‐scanning electron micrographs (FE‐SEM) and elemental mapping. The electrocatalytical activity of Pt thin film was investigated in methanol oxidation reaction.     

Platinum and Palladium Complexes Bearing New (1R,2R)‐(–)‐1,2‐Diaminocyclohexane (DACH)‐Based Nitrogen Ligands: Evaluation of the Complexes Against L1210 Leukemia

The reaction of (1R,2R)‐(–)‐1,2‐diaminocyclohexane ( 1 ) [DACH] with the aldehyde (1R)‐(–)‐myrtenal ( 2 ) in MeOH afforded the bidentate diimine ligand, (1R,2R)‐(–)‐N¹,N²‐bis{(1R)‐(–)myrtenylidene}‐1,2‐diaminocyclohexane ( 3 ) in a high yield. Reduction of 3 using LiAlH₄ led to the formation of the desired ligand ( 4 ) (1R,2R)‐(–)‐N¹,N²‐bis{(1R)‐(–)myrtenyl}‐1,2‐diaminocyclohexane. Treatment of compound 4 with K₂PtCl₄ or K₂PdCl₄ yielded the corresponding platinum(II) and palladium(II) complexes, Pt‐5 and Pd‐6 , respectively. The reaction of compound 3 with K₂PtCl₄ gave the diimine complex Pt‐7 . The cytotoxic activity of the complexes Pt‐5 , Pd‐6 and Pt‐7 was tested and compared to the approved drugs, cisplatin ( Cis ‐Pt ) and oxaliplatin ( Ox‐Pt ). The complexes ( Pt‐5 , Pd‐6 and Pt‐7 ) inhibit L1210 cell line proliferation with an IC₅₀ of 0.6, 4.2, and 0.7 μL, respectively as evidenced by measuring thymidine incorporation.     

Crystallization experiments with the dinuclear chelate ring complex di‐μ‐chlorido‐bis[(η2‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC1)platinum(II)]

Crystallization experiments with the dinuclear chelate ring complex di‐μ‐chlorido‐bis[(η²‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC¹)platinum(II)], [Pt₂(C₁₅H₁₉O₄)₂Cl₂], containing a derivative of the natural compound eugenol as ligand, have been performed. Using five different sets of crystallization conditions resulted in four different complexes which can be further used as starting compounds for the synthesis of Pt complexes with promising anticancer activities. In the case of vapour diffusion with the binary chloroform–diethyl ether or methylene chloride–diethyl ether systems, no change of the molecular structure was observed. Using evaporation from acetonitrile (at room temperature), dimethylformamide (DMF, at 313 K) or dimethyl sulfoxide (DMSO, at 313 K), however, resulted in the displacement of a chloride ligand by the solvent, giving, respectively, the mononuclear complexes (acetonitrile‐κN)(η²‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC¹)chloridoplatinum(II) monohydrate, [Pt(C₁₅H₁₉O₄)Cl(CH₃CN)]·H₂O, (η²‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC¹)chlorido(dimethylformamide‐κO)platinum(II), [Pt(C₁₅H₁₉O₄)Cl(C₂H₇NO)], and (η²‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC¹)chlorido(dimethyl sulfoxide‐κS)platinum(II), determined as the analogue {η²‐2‐allyl‐4‐methoxy‐5‐[(ethoxycarbonyl)methoxy]phenyl‐κC¹}chlorido(dimethyl sulfoxide‐κS)platinum(II), [Pt(C₁₄H₁₇O₄)Cl(C₂H₆OS)]. The crystal structures confirm that acetonitrile interacts with the Pt^II atom via its N atom, while for DMSO, the S atom is the coordinating atom. For the replacement, the longest of the two Pt—Cl bonds is cleaved, leading to a cis position of the solvent ligand with respect to the allyl group. The crystal packing of the complexes is characterized by dimer formation via C—H…O and C—H…π interactions, but no π–π interactions are observed despite the presence of the aromatic ring.     

Unprecedented 1D Mixed-metal Polynuclear Cyclometalated Platinum Complexes： Synthesis, Structural Characterization and Spectroscopic Properties

The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane, have been synthesized and characterized. In complex 1 the platinum（Ⅱ） center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a ＂stairstep＂ configuration with one-dimensional Pt（Ⅱ）N^N^CPO- Li（Ⅰ）-OPC^N^ NPt（Ⅱ） mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325（2） and 3.1432（9） A, respectively, and display strong metal-metal-to-ligand charge-transfer （MMLCT） triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.     

A novel cadmium(II) coordination polymer with biphenyl‐3,3′,4,4′‐tetra­carboxylic acid and 4,4′‐bipyridine

A novel cadmium(II) coordination polymer, poly[[[bis­(4,4′‐bipyridine)cadmium(II)]‐μ₃‐4,4′‐dicarboxy­biphenyl‐3,3′‐di­carboxyl­ato] 0.35‐hydrate], {[Cd(C₁₆H₈O₈)(C₁₀H₈N₂)₂]·0.35H₂O}_n, was obtained by reaction of Cd(CH₃COO)₂·3H₂O, 4,4′‐bipyridine (4,4′‐bpy) and biphenyl‐3,3′,4,4′‐tetra­car­boxylic acid (H₄L) under hydro­thermal conditions. Each Cd^II atom lies at the centre of a distorted octa­hedron, coordinated by four O atoms from three H₂L²⁻ ligands and N atoms from two monodentate 4,4′‐bpy ligands. Each H₂L²⁻ ligand coordinates to three Cd^II atoms through two carboxyl­ate groups, one acting as a bridging bidentate ligand and the other in a chelating bidentate fashion. Two Cd atoms, two H₂L²⁻ anions and four 4,4′‐bpy ligands form a ring dimer node, which links into an extended broad zonal one‐dimensional chain along the c axis.     

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.     

cis‐ and trans‐Dichloro(3,6‐dihydro‐1,2‐oxazine‐N)(dimethyl sulfoxide‐S)‐platinum(II)

Both the cis, (I), and trans, (II), isomers of the title complex, [PtCl₂(C₄H₇NO)(C₂H₆OS)], possess relatively undistorted square‐planar geometries about the Pt atoms. For (I), cisL—Pt—L angles are in the range 88.8 (2)–91.08 (8)°, while trans angles are 178.61 (8) and 179.4 (2)°. For (II), cisL—Pt—L 86.1 (3)–93.7 (1)°, and transL—Pt—L 175.5 (1) and 179.1 (3)°. The di­methyl sulfoxide (dmso) ligand adopts a normal pyramidal geometry in both complexes. In (I), the S=O bond essentially eclipses the adjacent Pt—N bond, while the oxazine ligand in (I) is twisted so as to avoid steric interactions with the adjacent chloride ligand. By contrast, the dmso ligand in (II) is rotated such that the S=O bond is approximately perpendicular to the square plane, while the oxazine ligand is once again twisted out of the plane by a similar amount as in (I). These are the first structural examples of square‐planar platinum(II) complexes containing a 1,2‐oxazine ligand.     

Carbon‐iodide bond activation by cyclometalated Pt (II) complexes bearing tricyclohexylphosphine ligand: A comparative kinetic study and theoretical elucidation

Cyclometalated Pt (II) complexes [PtMe(C^N)(L)], in which C^N = deprotonated 2,2′‐bipyridine N‐oxide (Obpy), 1 , deprotonated 2‐phenylpyridine (ppy), 2 , deprotonated benzo [h] quinolone (bzq), 3 , and L = tricyclohexylphosphine (PCy₃) were prepared and fully characterized. By treatment of 1–3 with excess MeI, the thermodynamically favored Pt (IV) complexes cis‐[PtMe₂I(C^N)(PCy₃)] (C^N = Obpy, 1a ; ppy, 2a ; and bzq, 3a ) were obtained as the major products in which the incoming methyl and iodine groups adopted cis positions relative to each other. All the complexes were characterized by means of NMR spectroscopy while the absolute configuration of 1a was further determined by X‐ray crystal structure analysis. The reaction of methyl iodide with 1–3 were kinetically explored using UV–vis spectroscopy. On the basis of the kinetic data together with the time‐resolved NMR investigation, it was established that the oxidative addition reaction occurred through the classical S_N2 attack of Pt (II) center on the MeI reagent. Moreover, comparative kinetic studies demonstrated that the electronic and steric nature of either the cyclometalating ligands or the phosphine ligand influence the rate of reaction. Surprisingly, by extending the oxidative addition reaction time, very stable iodine‐bridged Pt (IV)‐Pt (IV) complexes [Pt₂Me₄(C^N)₂(μ‐I)₂] (C^N = Obpy, 1b ; ppy, 2b ; and bzq, 3b ) were obtained and isolated. In order to find a reasonable explanation for the observation, a DFT (density functional theory) computational analysis was undertaken and it was found that the results were consistent with the experimental findings.     

Tuning the Excited—state Properties of Cyclometalated Platinum（Ⅱ）Complexes of 6—Pheny1—2,2’bipyridine by Ancillary Acetylide Ligand

A series of luminescent cyclometalated platinum(Ⅱ）complexes,(C^N^N)Pt(C≡CR)[HC^N^N=4-(4-tolyl)-6-phenyl-2,2’-bipyridine;R=4-chlorophenyl(1),phenyl(2) and 4-tolyl(3)],were synthesized,and their spectroscopic properties have been examined.These complexes are brightly emissive both in fluid solution and in the solid state,attributed to triplet metal-to-ligand charge transfer(^3MLCT)state.The excited state energy can be tuned by ancillary acetylide ligands.The emission lifetimes in dichloromethand solution at room temperature were up to 1.64 μs and the emission quantum yields were in the range of 0.03-0.15.     

Diverse Coordinative Functions of 4,4′‐Bipyridine Generating Abundant Weak Interactions and Novel Fluorescent Property in Cadmium(II)‐4‐sulfobenzoate Polymer

The cadmium(II) 4‐sulfobenzoate complex with 4,4′‐bipyridine, {[Cd₂(4,4′‐bipy)₄(4‐sb)₂(H₂O)₃] · 4H₂O}_n, has been synthesized and characterized by elemental analysis, IR, DTA‐TG, fluorescence analysis, powder X‐ray analysis, and single‐crystal X‐ray structural determination. Structural analysis showed that the complex contains two Cd atoms in an unsymmetrical unit. The Cd1 atom displays a seven‐coordinated geometry, which is a capped anti‐trigonal prismatic structure, whereas the Cd2 atom has an octahedral coordination. The 4,4′‐bipyridine ligands in the complex have three coordination behaviors, i.e., monodentate, dimeric linker, and polymeric bridge, which is the first example showing three coordinative functions for 4,4′‐bipyridine ligands in one complex. Moreover, three coordinative functions of 4,4′‐bipyridine ligands in this polymer lead to abundant weak interactions and novel fluorescent properties, which is benefit for design and preparation of functional materials in specific usage.