Four Zn(II)/Cd(II) coordination polymers derived from isomeric benzenedicarboxylates and 1,6-bis(triazol)hexane ligand: synthesis,crystal structure,and luminescent properties

Four coordination polymers, [Zn(o-bdc)(bth)_0.5(H₂O)] _n (1), [Cd(o-bdc)(bth)_0.5(H₂O)] _n (2), [Zn(m-bdc)(bth)] _n (3), and [Cd(p-bdc)(bth)?·?(H₂O)₂] _n (4) (where o-bdc?=?1,2-benzenedicarboxylate, m-bdc?=?1,3-benzenedicarboxylate, p-bdc?=?1,4-benzenedicarboxylate, and bth?=?1,6-bis(triazol)hexane), have been hydrothermally synthesized and structurally characterized. Both 1 and 2 are isostructural, featuring two binodal architectures: (6³)(6⁵·8) topology in terms of o-bdc and Zn^II/Cd^II as three- and four-connected nodes. Complex 3 shows a 2-D (4,4) network with the Zn?···?Zn?···?Zn angle of 57.84°, whereas 4 exhibits planar 2-D (4,4) network. These 2-D networks of 3 and 4 are extended by supramolecular interactions, such as CH?···?π/π–π stacking and hydrogen-bonding into 3-D architecture. A structural comparison of these complexes demonstrates that the dicarboxylate building blocks with different dispositions of the carboxyl site play a key role in governing the coordination motifs as well as 3-D supramolecular lattices. Solid-state properties such as photoluminescence and thermal stabilities of 1–4 have also been studied.     

1-D wave-like chain,twofold 2-D layer,and chiral 3-D open framework based on multidentate ligand: structural diversities,thermal properties,and photoluminescence

From 1-D to 3-D zinc coordination polymers based on multifunctional flexible 4-(1,2,4-triazole-methylene)-benzonitrile (tzbt), {[Zn(tzbt)₂(bdc)]·2H₂O}_n (1), [Zn(tzbc)₂]_n (2), and [Zn(bpdc)(H₂O)]_n (3) (bdc = 1,4-benzenedicarboxylic acid, tzbc = 4-(1,2,4-triazole-methylene)-benzoic acid, bpdc = 4,4′-biphenyldicarboxylic acid), were synthesized under hydrothermal conditions. The tzbt was synthesized by N-alkylation and hydrolyzed in situ to produce tzbc (in 2). Single-crystal X-ray diffraction analysis reveals that 1 displays 1-D wave-like chains based on [Zn(bdc)]_n. 2 is a chiral twofold interpenetrating 2-D architecture constructed with “V”-shaped tzbc. 3 is a 3-D chiral compound constructed from achiral H₂bpdc with right-handed helical chains. 1–3 display stable blue-emitting luminescence with emission maxima ranging from 383 to 410 nm, depending on ligand-centered π*→π transitions. The effects of different polarity solvents and temperature on luminescence are discussed. TGA and VT-XPRD reveal that 2 has thermal stability to 360 °C.     

Construction of two interpenetrating coordination networks based on 4,4′-bis(1H-imidazol-1-yl-methyl)biphenyl and effect of carboxylic acids

To investigate the construction of interpenetrating coordination networks and the effect of ligands, [Zn(bimb)(bdc)]·H₂O (1) and [Zn(bimb)(Hbtc)]·H₂O (2) [bimb?=?4,4′-bis(1H-imidazol-1-yl-methyl)biphenyl; H₂bdc?=?1,2-benzenedicarboxylic acid; H₃btc?=?1,3,5-benzenetricarboxylic acid] were hydrothermally synthesized and characterized by elemental analysis, IR spectra, Powder X-ray diffraction, and thermogravimetric analysis. Complex 1 shows a 3-D uoc type topology with twofold interpenetration. However, 2 exhibits a different 2-D self-penetrating network owing to hydrogen bonds of Hbtc between the two interpenetrating sql sheets, indicating that different carboxylic ligands could affect the interpenetration structures. Photoluminescence of bimb and the two complexes are also studied.     

Two Unusual Two‐dimensional (4,4) Network Cadmium Coordination Polymers Based on Flexible Bis(triazole) and Rigid Benzenedicarboxylate Co‐ligands

Two cadmium(II) coordination polymers {[Cd(btp)(NO₂‐1,3‐bdc)(H₂O)]·H₂O}_n ( 1 ) and {[Cd(btp)(1,2‐bdc)(H₂O)]·H₂O}_n ( 2 ) were synthesized by the reaction of 1,3‐bis(1,2,4‐triazol‐1‐yl)propane (btp), 5‐nitroisophthalate (NO₂‐1,3‐bdc), and 1,2‐benzenedicarboxylate (1,2‐bdc). 1 consists of undulated 2D (4,4) networks. Two identical undulated layers are parallel stacking to give a (2D→2D) polythreaded 2D network. A 3D supramolecular architectute is constructed through the hydrogen bond interactions. 2 has an unusual 2D (4,4) network with a thickness of ca. 10 Å. The btp ligands exhibit the anti‐gauche conformation in 1 and the anti‐anti conformation in 2 . The flexible btp ligand exhibits the key role in the assembly of the topologies of 1 and 2 . The luminescence and thermal stability were investigated.     

Synthesis,structures, and characterization of cadmium(II), cobalt(II), and copper(II) metal polymers with tetrazole-1-acetate

Three new coordination polymers {[Cd(tza)(2,2′-bpy)(H₂O)](ClO₄)} _n 1, {[Co(tza)(2,2′-bpy)(H₂O)](ClO₄)} _n 2, and {[Cu(tza)(phen)](ClO₄)} _n 3 (Htza = tetrazole-1-acetic acid, 2,2′-bpy = 2,2′-bipyridyl, phen = 1,10-phenanthroline) were synthesized and characterized by X-ray single-crystal diffraction, elemental analysis, and IR spectra. Complexes 1 and 2 exhibit 3-D architectures formed by π–π interaction of 2,2′-bpy ligands interlinking to the adjacent 2-D layers. Complex 3 is a 1-D zigzag double chain and the 3-D structure is formed by π–π stacking interaction of phen and nonclassical hydrogen bonding.     

Syntheses,structures, and properties of two 2-D Cd(II) complexes based on 2-(1H-imidazol-1-methyl)-1H-benzimidazole and polycarboxylate ligands

Two 2-D Cd(II) complexes, {[Cd(imb)(bdc)(H₂O)]·CH₃OH}_n (1) and {[Cd(imb)(Hbtc)(CH₃OH)]·2H₂O·CH₃OH}_n (2), have been synthesized by reactions of CdCl₂·2.5H₂O with 2-(1H-imidazol-1-methyl)-1H-benzimidazole (imb) and 1,3-benzenedicarboxylic acid (H₂bdc) or 1,3,5-benzenetricarboxylic acid (H₃btc). Single-crystal X-ray diffraction shows that 1 possesses an infinite 2-D layered structure in which all the carboxylates chelate Cd(II) and imb bridge Cd(II) ions. Complex 2 also features an infinite 2-D layered structure and imb ligands also bridge Cd(II) ions, but two carboxylates of each 1,3,5-benzenetricarboxylate coordinate to Cd(II) in monodentate or chelating mode, leaving the third one, which is not deprotonated, uncoordinated. IR spectra, fluorescent properties, and thermogravimetric analyses of both complexes have been investigated.     

Coordination Frameworks based on 3,5‐Bis(imidazole‐1‐yl)­pyridine and Aromatic Dicarboxylate Ligands: Synthesis,Crystal Structures,and Photoluminescent Properties

Three metal coordination polymers [Zn(bdc)(L)(H₂O)]_n ( 1 ), [Co(pta)(L)(H₂O)₂]_n ( 2 ), and [Cd(tda)(L)(H₂O)]_n ( 3 ) [H₂bdc = 1,2‐benzene dicarboxylate acid, H₂pta = terephthalic acid, H₂tda = 2,5‐thiophenedicarboxylic acid, L = 3,5‐bis(imidazole‐1‐yl)pyridine] were synthesized and structurally characterized by IR spectroscopy, elemental analysis, X‐ray powder diffraction, and X‐ray single crystal diffraction. Complex 1 shows a three‐dimensional (3D) structure with cco topology with the symbol 6⁵ · 8, whereas complex 2 features a 3D structure with cds topology with the symbol 6⁵ · 8. Complex 3 has a 2D network constructed by the cadmium atoms bridged through the ligands tda and L. Their X‐ray powder diffraction patterns were compared with the simulated ones. Moreover, their luminescent properties were investigated in the solid state at room temperature, and the thermogravimetric analyses were carried out to study the thermal stability of the 3D networks.     

Architectural diversity of six coordination compounds based on (S)-(+)-mandelic acid and different N-donor auxiliary ligands: syntheses,structures, and luminescent properties

Six transition metal coordination compounds with H₂mand and different N-donor ligands, [Co(Hmand)₂(2,2′-bipy)]·H₂O (1), [Ni(Hmand)₂(2,2′-bipy)]·H₂O (2), [Ni(Hmand)₂(bpe)] (3), [Zn(Hmand)₂(2,4′-bipy)(H₂O)]·2H₂O (4), [Zn(Hmand)(bpe)(H₂O)]_n[(ClO₄)]_n·nH₂O (5), and [Zn(Hmand)(4,4′-bipy)(H₂O)]_n[(ClO₄)]_n (6), were synthesized under different conditions (H₂mand = (S)-(+)-mandelic acid, bpe = 1,2-di(4-pyridyl)ethane, 4,4′-bipy = 4,4′-bipyridine, 2,4′-bipy = 2,4′-bipyridine, 2,2′-bipy = 2,2′-bipyridine). Their structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, infrared spectra, thermogravimetric analysis, powder X-ray diffraction, and circular dichroism. Compounds 1 and 2 are isostructural (0-D structures), which are extended to supramolecular 1-D chains by hydrogen bonding. Compound 3 exhibits 1-D straight chain structures, which are further linked via hydrogen bond interactions to generate a 3-D supramolecular architecture. Compound 4 displays a discrete molecular unit. Neighboring units are further linked by hydrogen bonds and π–π interactions to form a 3-D supramolecular architecture. Compound 5 displays a 2-D undulated network, further extended into a 3-D supramolecular architecture through hydrogen bond interactions. Compound 6 possesses a 2-D sheet structure. Auxiliary ligands and counteranions play an important role in the formation of final frameworks, and the hydrogen-bonding interactions and π–π stacking interactions contributed to the formation of the diverse supramolecular architectures. Compounds 1, 2, 4, 5, and 6 crystallize in chiral space groups, with the circular dichroism spectra exhibiting positive cotton effects. Furthermore, the luminescent properties of 4–6 have been examined in the solid state at room temperature, and the different crystal structures influence emission spectra significantly.     

Syntheses,structures, and properties of two- and three-dimensional coordination polymers based on bis(imidazole) and glutarate ligands

Two new coordination polymers, [Zn(bix)_0.5(glu)]_n (1) and {[Co(bix)(glu)]·4H₂O}_n (2), were synthesized (bix = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene, glu = glutarate). In 1, each Zn(II) is connected by four glu ligands and extend to form a [Zn(glu)]_n 2-D network. Adjacent [Zn(glu)]_n 2-D networks are bridged by bix ligands to construct a 6-connected 3-D network based on the Zn₂ unit. 2 shows an undulated 2-D (4,4) network. The interesting structural feature of 2 is that there are 1-D water chains. The O–H···O hydrogen bond interactions link the 2-D coordination networks and construct the 3-D supramolecular architecture in 2. The glu ligands are bis-(bidentate) bridges in 1 and bis-(monodentate) bridges in 2. The luminescence of 1 and thermal stability of 1 and 2 were investigated.     

Synthesis,Structures, and Properties of two Helical Structures from Rigid Carboxylate Ligand and Flexible N‐Bridging Ligands

Two novel coordination polymers based on mixed ligands, [Zn(dpb)(bdc)(H₂O)]_n ( 1 ) and [Cd(dpb)(bbdc)(H₂O)(DMF)]_n ( 2 ) [dpb = 1, 4‐bis(pyridin‐3‐ylmethoxy)benzene, H₂bdc = 1, 4‐benzenedicarboxylate, H₂bbdc = 4, 4′‐dibenzenedicarboxylate], were synthesized under hydrothermal conditions. Compound 1 forms meso‐helical chain and shows three fold interpenetrating architecture with 4‐connected net {6 6} diamond topology. Compound 2 is a left‐ and right‐handed helical layer, which are interacted by π–π stacking interactions to construct a 3D framework. The luminescent properties of the compounds are discussed.     

Ferromagnetic copper(II)–copper(II) interaction in a single chlorido and dicyanamido bridged mixed–valence copper(I/II) 2-D polymer generated by in situ partial reduction of copper(II)

A mixed-valence 2-D Cu(I/II) complex, [{Cu(II)(dmen)(μ-Cl)(μ_1,5-dca)}{Cu(I)(μ_1,5-dca)}]_n (1) (dmen = N,N-dimethylethylenediamine, dca = dicyanamide = [N(CN)₂]^?), has been synthesized by in situ partial reduction of Cu(II) to Cu(I) using benzoin (2-hydroxy-1,2-di(phenyl)ethanone) as reductant. Complex 1 was characterized by spectroscopic techniques, single crystal X-ray diffraction, and low temperature magnetic measurements. Structural investigation reveals that 1 represents a mixed-valence 2-D coordination polymer formed by parallel 1-D [Cu(II)(dmen)(Cl)Cu(I)(μ_1,5-dca)₂]_n chains running along the b axis, where chloride bridges Cu(II) ions of adjacent polymers through long connections (2.8401(1) Å) to form a 2-D network. The metal centers have two different geometrical environments (distorted square pyramidal and distorted trigonal planar geometries for Cu(II) and Cu(I), respectively). The Cu(II) ions in [Cu(II)(dmen)(μ-Cl)(dca)]_n are interconnected through single chloride bridges while within the [Cu(I)(μ_1,5-dca)]_n units, the dca connects adjacent Cu(I) ions through μ_1,5-dca bridges. Magnetic susceptibility measurements reveal weak ferromagnetic interactions (J = +0.3 cm^?1) within the chlorido-bridged Cu(II) regular chain present in 1. Simultaneous presence of μ_1,5-dca and single chlorido bridges with ferromagnetic coupling is believed to be unique in mixed-valence Cu(I)/Cu(II) complexes.     

Copper(II) coordination polymers constructed from aromatic polycarboxylate and flexible triazole ligands with different spacer lengths: syntheses,structures, and properties

{[Cu₂(btm)₂(Hbtc)(H₂btc)₂(H₂O)]·9.5H₂O}_n (1), [Cu(bte)(H₂btc)₂]_n (2) {[Cu(btp)(H₂btc)₂]·0.25H₂O}_n (3) (btm?=?bis(1,2,4-triazol-1-yl)methane, bte?=?bis(1,2,4-triazol-1-yl)ethane, btp?=?bis(1,2,4-triazol-1-yl)propane, H₃btc?=?benzene-1, 3, 5-tricarboxylic acid) have been synthesized and structurally characterized. 1 features a 1-D double chain, which is interconnected by classical hydrogen-bonding (O–H?O) and π–π interactions to lead to a 3-D supramolecular architecture. 2 and 3 are both 1-D single chains, which are interconnected by π–π interactions to 2-D layer architectures. Elemental analysis, XRD, IR, TG and EPR spectra have been carried out and discussed.     

Syntheses,crystal structures,and photophysical properties of two 2-D coordination polymers with different geometries of lead(II)

Two complexes constructed from aromatic acid and N-heterocyclic ligands have been synthesized by hydrothermal reaction: [Pb(cipt)(NDC)]_n (1) [cipt?=?2-(3-chlorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, NDC?=?naphthalene-1,4-dicarboxylic acid] and [Pb(ipm)(BDC)₂]_n (2) [BDC?=?terephthalic acid, ipm?=?5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-2-methoxyphenol]. Single-crystal X-ray analysis shows that 1 exhibits an interesting arm-shaped chain structure. 1-D ladder chain structure is formed by N–H···O bonding interactions and further into a 2-D network by N–H···O hydrogen bonds and interchain π–π stacking interactions. Complex 2 shows a 2-D butterfly wings structure, which has been rarely reported. The structure in 2 has intermolecular N–H···O interactions, which help in construction of the 3-D framework. In 1, the coordination sphere of Pb(II) is hemi-directed, whereas the Pb(II) geometry in 2 is holo-directed. The solid-state fluorescence spectra of 1 and 2 are also investigated, as well as the ligands cipt and ipm.     

Two independent, 1-D metal–organic nanotubes based on rings or helical chain units

Three coordination polymers {[Mn(bte)(NO₂-1,3-bdc)(H₂O)]·H₂O}_n (1), {[Mn(btp)(NO₂-1,3-bdc)(H₂O)]·2H₂O}_n (2), and {[Mn(btb)(NO₂-1,3-bdc)(H₂O)]·H₂O}_n (3) (bte, 1,2-bis(1,2,4-triazol-1-yl)ethane; btp, 1,3-bis(1,2,4-triazol-1-yl)propane; btb, 1,4-bis(1,2,4-triazol-1-yl)butane, NO₂-1,3- H₂bdc, 5-nitroisophthalic acid) were synthesized by combination of bte, btp, and btb, conformationally flexible ligands with different spacer lengths, and the rigid [NO₂-1,3-bdc]^2?. In 1, two [NO₂-1,3-bdc]^2? anions link adjacent [Mn₂(bte)₂] rings to give an independent, 1-D metal–organic nanotube (MONT). The structure of 2 is an undulating 2-D (4,4) network. In 3, the combination of a [Mn(btb)]_n single helical chain and two [Mn(NO₂-1,3-bdc)]_n linear chains assemble an intriguing independent, 1-D MONT. An interesting structural feature of 1 and 3 is that the nitro groups of each 1-D MONT interpenetrate into two adjacent 1-D MONTs to form a 1-D → 2-D interdigitated array. 3-D architectures in 1 and 3 are assembled via hydrogen bond interactions. The luminescent properties and thermal stabilities of 1, 2, and 3 were investigated.     

Hydrothermal synthesis,crystal structure and fluorescence of a cyclic dimer copper compound constructed by 2-nitrobenzenedicarboxylate

The reaction of 2-nitro-1,4-benzenedicarboxylic acid (H₂nbdc) and 2,2′-bipyridine (2,2′-bipy) with CuCl₂ under hydrothermal conditions gives rise to a cyclic dimer [Cu(nbdc)(2,2′-bipy)(H₂O)]₂ · 2H₂O (1). X-ray structural analysis revealed that 1 crystallizes in a monoclinic space group P2₁/c with a = 7.3801(13) Å, b = 15.305(3) Å, c = 16.333(3) Å, β = 92.951(4)°, V = 1842.5(6) ų, and Z = 2. Compound 1 represents the first cyclic dimeric example with 1,4-benzenedicarboxylate or its derivatives, in which two carboxylates of the nbdc are nearly perpendicular due to the steric effect by the nitro group. Compound 1 also displays strong fluorescent emission in the solid state.     

Dinuclear copper(II) complex and 1-D copper(II) complex with taurine Schiff base: synthesis,crystal structure,and properties

A dinuclear copper(II) compound, [Cu(btssb)(H₂O)]₂ · 4(H₂O) (1), and a 1-D chain copper(II) compound, [Cu(ctssb)(H₂O)] _n (2) [where H₂btssb is 2-[(5-bromo-2-hydroxy-benzylidene)-amino]-ethanesulfonic acid and H₂ctssb is 2-[(3,5-dichloro-2-hydroxy-benzylidene)-amino]-ethanesulfonic acid], were prepared and characterized. Compound 1 crystallizes in the monoclinic space group P2₁/c, with a = 10.109(2) Å, b = 20.473(4) Å, c = 6.803(1) Å, β = 100.32(3)°, V = 1385.1(5) ų, and Z = 2; R ₁ for 1796 observed reflections [I > 2σ(I)] was 0.0357. The geometry around each copper(II) can be described as slightly distorted square pyramidal. The Cu^II ··· Cu^II distance is 5.471(1) Å. Compound 1 formed a 1-D network through O–H ··· O hydrogen bonds and 1-D water chains exist. The 1-D chain complex 2 crystallizes in the triclinic space group P 1, with a = 5.030(2) Å, b = 7.725(2) Å, c = 17.011(5) Å, α = 92.706(4)°, β = 97.131(4)°, γ = 102.452(3)°, V = 638.6(3) ų, and Z = 2; R ₁ for 1897 observed reflections [I > 2σ(I)] was 0.0171. In 2, Cu(II) was also a slightly distorted square pyramid formed by two oxygens and one nitrogen from ctssb, one oxygen from another ctssb, and one water molecule. The complex formed a 1-D chain through O–S–O bridge of ctssb ligand. The 1-D chain further constructed a double chain through O?H ··· O hydrogen bonds.     

Four Cu(II)/Co(II) coordination polymers based on N,N′-di(3-pyridyl)sebacicdiamide: influence of different carboxylate ancillary ligands on structures and properties

Four Cu(II)/Co(II) coordination polymers, [Cu(L)(BDC)(H₂O)]·3H₂O (1), [Cu(L)(DNBA)₂] (2), [Co(L)₂(DNBA)₂] (3), and [Co(L)(NIPH)(H₂O)]·H₂O (4) (H₂BDC = 1,4-benzenedicarboxylic acid, HDNBA = 3,5-dinitrobenzoic acid, H₂NIPH = 5-nitroisophthalic acid, L = N,N′-di(3-pyridyl)sebacicdiamide), have been synthesized under hydrothermal conditions. The structures of 1–4 have been determined by single-crystal X-ray diffraction analyses and 1–4 were further characterized by infrared spectroscopy and thermogravimetric analyses. Complex 1 is a 2-D polymeric layer with a 4-connected sql topology. Complex 2 displays a 1-D zigzag chain. Complex 3 possesses a 1-D double-chain structure. Complex 4 exhibits a ribbon chain based on the 1-D [Co–L]_nmeso-helical chain. Adjacent layers for 1 and adjacent chains for 2–4 are further linked by hydrogen bonding or π–π stacking interactions to form 3-D supramolecular networks. The differences of carboxylates and metal ions show significant effect on the ultimate architectures of the four complexes. Thermal stabilities, fluorescent properties and photocatalytic activities of 1–4 were also studied.     

Two manganese(II) complexes constructed from 2-(3-pyridyl)-imidazo[4,5-f] 1,10-phenanthroline and organic dicarboxylates: syntheses,crystal structures,and luminescence

In this study, two new Mn(II) complexes consisting of a phenanthroline derivative and organic acid ligands, [Mn(3-PIP)(1,3-bdc)] _n (1) and [Mn(3-PIP)₂(1,4-bdc)] _n (2) (3-PIP?=?2-(3-pyridyl)-imidazo[4,5-f]?1,10-phenanthroline, 1,3-H₂bdc?=?benzene-1,3-dicarboxylic acid, 1,4-H₂bdc?=?benzene-1,4-dicarboxylic acid), have been synthesized via hydrothermal reaction and characterized by Fourier transform infrared (FT-IR) spectra, elemental analyses, and single-crystal X-ray diffraction. Complex 1 is a one-dimensional (1-D) twisted double chain bridged by 1,3-bdc. The 3-PIP ligands in a parallel fashion are alternately attached to both sides of the 1-D double chain. Complex 2 exhibits a 1-D zigzag chain, to which pairs of crossed 3-PIP ligands are alternately attached. The two complexes are further extended into three-dimensional (3-D) supramolecular structures by hydrogen-bonding and π–π stacking interactions. The N-donor ligands with an extended π-system play a crucial role in formation and stabilization of the final supramolecular frameworks. Thermal properties of 1 and 2 and fluorescence of 2 are investigated in the solid state.     

One‐ and Two‐Dimensional PbII Complexes Constructed from N‐Donor Chelating Ligands with Extended π‐System and Organic Dicarboxylates

Two new coordination polymers [Pb(TIP)(1,3‐bdc)]_n ( 1 ) and [Pb(Dpq)(fum)]_n ( 2 ) (TIP = 2‐(2‐thienyl)imidazo[4,5‐f]1,10‐phenanthroline, Dpq = dipyrido[3,2‐d:2′,3′‐f]quinoxaline, 1,3‐H₂bdc = benzene‐1,3‐dicarboxylic acid, fum = fumaric acid) were synthesized by hydrothermal reactions and were characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. Complex 1 is a one‐dimensional (1D) chain, which is bridged by 1,3‐bdc ligands. This is further extended into a three‐dimensional (3D) supramolecular structure by hydrogen bonding interactions. Compound 2 exhibits a two‐dimensional (2D) network structure, which is further stacked by π–π interactions to form a 3D supramolecular framework. The most important feature of these two complexes is that the N‐donor ligands with an extended π‐system play a crucial role in the formation and stabilization of the final supramolecular frameworks. Moreover, the fluorescence property of complex 1 was also investigated in the solid state at room temperature.     

Supramolecular networks constructed by cationic copper(II) complexes incorporating hybrid water–anionic polymeric assemblies

Two complexes, [Cu₂(TFSA)(2,2′-bpy)₄]?·?TFSA?·?8H₂O (1) and {[Cu(4,4′-bpy)(H₂O)₂]?·?TFSA?·?6H₂O} _n (2) (H₂TFSA?=?tetrafluorosuccinic acid, 2,2′-bpy?=?2,2′-bipyridine, and 4,4′-bpy?=?4,4′-bipyridine), have been synthesized and structurally characterized by X-ray structural analyses. Complex 1 is a binuclear molecule bridged by TFSA ligands; 2 is a 1-D chain bridged by 4,4′-bpy ligands. The asymmetric units of the two complexes are composed of cationic complexes [Cu₂(TFSA)(2,2′-bpy)₄]²⁺ (1) and [Cu(4,4′-bpy)(H₂O)₂]²⁺ (2), free TFSA anion, and independent crystallization water molecules. A unique 2-D hybrid water–TFSA anionic layer by linkage of {[(H₂O)₈(TFSA)]^2?} _n fragments consisting of 1-D T6(0)A2 water tape and TFSA anionic units by hydrogen bonds in 1 was observed. Unique 2-D hybrid water–TFSA anionic layer generated by the linkage of {[(H₂O)₆(TFSA)]^2?} _n fragments consisting of cyclic water tetramers with appended water molecules and TFSA anionic units, and 1-D metal–water tape [Cu–H₂O?···?(H₂O)₆?···?H₂O^?] _n in 2 were found. 3-D supramolecular networks of the two complexes consist of cationic complexes and water–TFSA anionic assemblies connected by hydrogen bonds.