Syntheses and structures of two zinc coordination polymers with a three-dimensional α-polonium cubic network and a two-dimensional (4,4) network

Two unusual zinc coordination polymers {[Zn(bim)₃](NO₃)₂·(H₂O)₄} _n (1) and {[Zn(bte)₂ (H₂O)₂](NO₃)₂} _n (2) [bim?=?1,2-bis(imidazol-1-yl)ethane, bte?=?1,2-bis(1,2,4-triazol-1-yl)ethane] were synthesized and characterized. 1 possesses a double interpenetrating three-dimensional α-polonium cubic network and 2 consists of a two-dimensional (4,4) network.     

Synthesis and electrochemical characterization of complexes of 1,2-bis[2-(pyridylmethylideneamino)phenylthio]ethanes with transition metals (CoII, NiII, CuII)

Transition metal (Ni^II, Co^II, and Cu^II) complexes with 1,2-bis[2-(3-pyridylmethylideneamino)phenylthio]ethane (1) and 1,2-bis[2-(4-pyridylmethylideneamino)phenylthio]ethane (2) were synthesized for the first time by slow diffusion of solutions of compounds 1 or 2 in CH₂Cl₂ into solutions of MX₂ · nH₂O (M = Ni, Co, or Cu; X = Cl or NO₃; n = 2 or 6) in ethanol. The reactions with Co^II and Cu^II chlorides afford complexes of composition M(L)Cl₂ (L = 1 or 2). The reactions of compound 1 with Ni^II salts produce complexes with 1,2-bis(2-aminophenylthio)ethane. The molecular structure of dinitrato[1,2-bis(2-aminophenylthio)ethane]nickel(ii) was confirmed by X-ray diffraction. The ligands and the complexes were investigated by cyclic voltammetry and rotating disk electrode voltammetry. The initial reduction of the complexes proceeds at the metal atom. The oxidation of the chlorine-containing complexes proceeds at the coordinated chloride anion. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–355, February, 2008.     

Four Novel 30-Membered Imine and Amine Macrocycles Derived from Ortho-Aminophenyl Diamines

Two novel macrocyclic tetra-imine-diphenol Schiff base (H₂L₁ and H₂L₂) were synthesized by [2 + 2] cyclocondensation of ortho-aminophenyl diamines [1,2-bis(2′-aminophenoxy)benzene (I) and 1,2-bis(2′-aminophenoxy)-4-t-butylbenzene (II)] with 2,6-diformyl-4-methylphenol. Two novel tetra-amine-diphenol macrocycles (H₂L₃ and H₂L₄) have been obtained by reduction of the imine analogs with NaBH₄ in MeOH/CHCl₃.     

Syntheses,structures, and characterizations of two coordination polymers assembled from zinc(II) salts with 1,2-bis[3-(1,2,4-triazolyl)-4-amino-5-carboxylmethylthio]ethane

Two new coordination polymers, [ZnL] _n (1) and {[Zn(phen)(L)(H₂O)]?·?3H₂O} _n (2) (H₂L?=?1,2-bis[3-(1,2,4-triazolyl)-4-amino-5-carboxylmethylthio]ethane, phen?=?1,10-phenanthroline), have been synthesized and characterized by elemental analysis, IR, and X-ray diffraction. Polymer 1 is a 1-D infinite chain (space group P 1) and further forms a 3-D supramolecular structure by S?···?S interactions and hydrogen bonds. Polymer 2 displays a mononuclear structure (space group P 1) and extends into a 3-D supramolecular structure through hydrogen bonds. In addition, spectra and thermal stability of 1 and 2 are also discussed. Strong luminescence characteristics of both polymers are found, suggesting their potential applications as luminescent materials.     

Syntheses and structures of three Mn(II) coordination polymers assembled from a dithiocarboxylic acid and N-donor ligands

Three new complexes, {[Mn(dtb)(bpe)·2H₂O]·H₂O} _n (1), {[Mn(dtb)(bpa)·2H₂O]·H₂O} _n (2), and {[Mn(dtb)(phen)]} _n (3) [H₂dtb?=?5,5′-dithiobis(2-nitrobenzoic acid), bpe?=?1,2-bis(4-pyridyl)ethene, bpa?=?1,2-bi(4-pyridyl)ethane, phen?=?1,10-phenanthroline], have been synthesized under hydrothermal conditions with Mn(OAc)₂·4H₂O, dtb, and different N-donor ligands. X-ray structure analyses of 1 and 2 reveal analogous structures with 1D helical chains and 2D 4⁴ chiral layers. The structure of 3 shows a 1D chain which is outwardly decorated with phen ligands. These neutral polymeric complexes exhibit structural diversity due to the different coordination modes of the flexible dtb ligand and the N-donor ligands. The thermogravimetric analyses and X-ray powder diffractions of 1–3 are also presented.     

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.     

基于芳香四羧酸构筑的两种配位聚合物的荧光及磁性质（英文）

在溶剂热条件下,基于芳香四羧酸合成了2种新颖的配位聚合物:{[Zn2(tptc)(1,4-bimb)2]·H2O}n(1)和{[Ni(tptc)0.5(1,2-bimb)(H2O)]·H2O}n(2),其中,tptc为对-三联苯-3,3″,5,5″-四羧酸,1,4-bimb为1,4-二(咪唑-1-亚甲基)苯,1,2-bimb为1,2-二(咪唑-1-亚甲基)苯。结构分析表明,1为三维结构,拓扑符号为(86);2为二维层状网络,通过氢键相互作用进一步扩展为三维超分子结构。此外,我们还研究了1对阳离子、阴离子的荧光感应以及2的磁性质。     

Design and syntheses of two threefold interpenetrating 2-D networks

Two new interpenetrating networks, [Ni(2,2′-bpy)(5-npa)(bpe)_0.5(H₂O)] _n (1) and [Ni(2,2′-bpy)(5-npa)(bpa)_0.5(H₂O)] _n (2) (2,2′-bpy?=?2,2′-bipyridine, 5-npa?=?5-nitroisophthalato, bpe?=?1,2-bis(4-pyridyl)ethylene, bpa?=?1,2-bis(4-pyridyl)ethane), have been synthesized and characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, X-ray powder diffraction, and single-crystal X-ray diffraction. Complexes 1 and 2 have similar structures and show a threefold interpenetrating topology constructed by three 2-D wave-like networks. Secondary building unit (SBU), [Ni(2,2′-bpy)(5-npa)(H₂O)] _n , was used as starting material of the multistep reaction. Replacing one coordination bond of chelating carboxyl group of SBUs by bpe and bpa afford the two threefold interpenetrating complexes.     

Large branched alkylthienyl bridged naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole-containing low bandgap copolymers: Synthesis and photovoltaic application

Two donor-acceptor (D-A) type low bandgap (LBG) alternating conjugated copolymers containing larger conjugation planarity and stronger electro-withdrawing ability naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole (NT) unit, namely, poly[4,8-bis(5-(n-octylthio)thien-2-yl)-benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-4,9-bis(4-(2-decyltetradecyl)thien-2-yl)naphtho- [1,2-c:5,6-c′]bis[1,2,5]thiadiazole-5,5′-diyl] (PBDT-TS-DTNT-DT) and poly[4,8-bis(triiso-propylsilylethynyl)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-4,9-bis(4-(2-decyltetradecyl)-thien-2-yl)naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole-5,5′-diyl] (PBDT-TIPS-DTNT-DT), were prepared by the palladium-catalyzed Stille polycondensation and characterized by gel permeation chromatography (GPC), UV-Vis absorption, thermal gravimetric analysis (TGA), cyclic voltammetry (CV) etc. PBDT-TS-DTNT-DT and PBDT-TIPS-DTNT-DT show the broader absorption and deeper highest occupied molecular orbital (HOMO) energy level approximately ?5.45 and ?5.62 eV, respectively. Bulk-heterojuction solar cells based on the resulted polymers and [6,6] phenyl-C₆₁ butyric acid methyl ester (PC₆₁BM) blends, with the device configuration of ITO/PFN/polymer:PC₆₁BM/MoO₃/Ag were prepared and investigated. The results showed the power conversion efficiency (PCE) of 2.67% for PBDT-TS-DTNT-DT/PC₆₁BM (w:w, 1:2) and 0.64% for PBDT-TIPS-DTNT-DT/PC₆₁BM (w:w, 1:1), with relatively high open-circuit voltage (V_OC) of 0.86 and 1.05 V, small short-circuit current (J_SC) of 5.41 and 0.97 mA cm^?2 and moderate fill factor (FF) of 57.8% and 62.4%, under an AM1.5 simulator (100 mWcm^?2), respectively.     

Syntheses,structures and photocatalytic degradation of organic dyes for two isostructural copper coordination polymers involving in situ hydroxylation reaction

Two copper(II) coordination polymers, {[Cu₂(btre)(hsuc)Cl(H₂O)]·1.5H₂O}_n (1) and {[Cu₂(btre)(hsuc)Br(H₂O)]·1.5H₂O}_n (2) (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane, H₃hsuc = 2-hydroxysuccinic acid), were synthesized by the hydrothermal method via in situ hydroxylation reaction with fumarate (fum), btre and CuCl₂/CuBr₂, and characterized by elemental analyses, IR, TG and X-ray diffraction. 1 and 2 are isostructural and show a 4-connected 2-D network based on [Cu₂O] dimers. 1 and 2 show good photocatalytic activity for the degradation of organic dyes methylene blue and methyl orange under UV light irradiation.     

Syntheses,crystal structures,and fluorescent properties of two Cd(II) complexes based on 2,2′-(ethane-1,2-diyl)bis(1H-imidazole-4,5-dicarboxylic acid)

Two new complexes, [Cd₂(H₄ebidc)₂(CH₃OH)₄]?·?2CH₃OH (1) and {[Cd(Cl)(I)(H₆ebidc)_1/2]?·?1/2bbe?·?H₂O} _n (2) (H₆ebidc?=?2,2′-(ethane-1,2-diyl)bis(1H-imidazole-4,5-dicarboxylic acid), bbe?=?1,2-bis(2-benzimidazolyl)ethane), are obtained through self-assembly of H₆ebidc with Cd(II). Single-crystal X-ray diffraction shows that 1 has a binuclear structure and each tridentate chelating ligand coordinates to two Cd(II) ions with µ₂-O. Complex 2 displays a 1-D chain structure and each tetradentate ligand bridges two Cd(II) ions in chelating fashion. Fluorescent properties have also been determined.     

Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part I

The synthesis and thermal behavior of the new [Pd(fum)(bipy)] _n ·2nH₂O (1), [Pd(fum)(bpe)] _n ·nH₂O (2) and [Pd(fum)(pz)] _n ·3nH₂O (3) {bipy = 4,4′-bipyridine, bpe = 1,2-bis(4-pyridyl)ethene and pz = pyrazine} fumarate complexes are described in this work as well their characterization by IR and ¹³C CPMAS NMR spectroscopies. TG curves showed that the compounds released organic ligands and lattice water molecules in the temperature range of 46–491 °C. In all the cases, metallic palladium was identified as the final residue.     

Two Cd(II) coordination polymers based on tris(p-carboxylphenyl)phosphine oxide accompanied by in situ ligand formation

Two Cd(II) coordination polymers constructed from tris(p-carboxylphenyl)phosphine oxide (H₃TPO), [Cd(HTPO)(1,4-bix)·3H₂O]_n (1) and [Cd₂(HTPO)(HBPO)(H₂O)₂]_n (2) (1,4-bix = 1,4-bis(imidazol-1-ylmethyl)benzene, H₃BPO = bis(4-carboxylphenyl)phosphinic acid), were synthesized and identified by IR, elemental analysis, and single-crystal X-ray diffraction analysis. The 1,4-bix ligand leads to 1 as a ladder-like 1D chain structure. In 2, adjacent Cd₂ units are bridged by HBPO^2– and HTPO^2– ligands to form a 3D structure. The H₃BPO ligand is formed from the in situ reaction of H₃TPO. It is the first example from hydrated Cd(II) salt promoting partial hydrolysis of a phosphine oxide ligand. The thermal behavior and solid-state photoluminescence properties correlated with the corresponding structural features were investigated.     

锌、镉配位聚合物的合成、晶体结构及荧光性质

通过水热法合成了2个金属-有机配位聚合物[Zn(boba)(bix)]n(1)和[Cd(L1)(L2)]2n·nH2O(2)(H2boba=4,4′-(丁烷-1,2-二氧基)-二苯甲酸,bix=1,4-双(咪唑基-1-基)苯,H2L1=4-(羧基甲氧基)苯甲酸,L2=2-(4-羟基)-1H-咪唑并[4,5-f][1,10]菲咯啉)。并对其进行了元素分析、红外光谱、热重和X-射线单晶衍射测定。配合物1为二维网状结构,配合物2为一维双链结构。此外,还研究了它们的荧光性质。     

Crystal structures and magnetic properties of three cobalt(II)–organic frameworks with nanoscale channels

Three cobalt(II) coordination polymers, {[Co(nip)(4,4′-bpy)] · 3H₂O} _n (1), [Co(nip)(bpe)] _n (2), and [Co(nip)(bpp)(H₂O)] _n (3), were hydrothermally synthesized by the reaction of cobalt nitrate hexahydrate and nip with 4,4′-bpy, bpe, and bpp [nip = 5-nitro-1,3-benzenedicarboxylato, 4,4′-bpy = 4,4′-bipyridine, bpe = 1,2-bis(4-pyridyl)ethane, bpp = 1,3-bis(4-pyridyl)propane], respectively. Co(II) displays different coordination in the three complexes, resulting in different structures with nanoscale channels. Compounds 1 and 2 form 2-D layer structures, but 3 has a two-fold interpenetrated 3-D framework. The magnetic properties associated with their crystal structures were investigated.     

Synthesis and structures of two cobalt(II) coordination networks formed from aromatic polycarboxylates and 1,4-bis(imidazole-1-ylmethyl)benzene

Two Co(II) coordination polymers, [Co(Hbtc)(bix)] _n , (1) and [Co(1,4-bdc)(bix)H₂O] _n (2) (bix = 1,4-bis(imidazole-1-ylmethyl)benzene; H₃btc = benzene-1,3,5-tricarboxylic acid; 1,4-H₂bdc = benzene-1,4-dicarboxylic acid) have been synthesized under hydrothermal conditions and structurally characterized. X-ray structure analysis reveals that in polymer 1, 2D infinite grid-like frameworks are interconnected by hydrogen-bond interactions to result in a 3D supramolecular architecture, in which the three carboxylate groups of the H₃btc molecule adopt three different coordination modes. In polymer 2, 1,4-bdc ligands with cobalt atoms construct 1D zigzag chains which are bridged by bix ligands to form a 3D framework.     

Synthesis and crystal structures of silver(I) and copper(II) complexes with <Emphasis Type="Italic">p</Emphasis>-xylylene-bridged bipyrazolyl ligands

Two semi-rigid bipyrazolyl ligands, namely 2,3,5,6-tetramethyl-1,4-bis[(3′,5′-dimethyl-1H -pyrazol-4′-yl)methylene]benzene (H₂L) and 2,3,5,6-tetramethyl-1,4-bis[(3′,5′-diphenyl-1H -pyrazol-4′-yl)methylene]benzene (H₂L′), and their Ag(I) and Cu(II) complexes have been prepared and structurally characterized by means of X-ray analysis. In the structures of the metal complexes, namely [Ag₂(H₂L)₂](BF₄)₂·2H₂O (1), [Ag(H₂L)(NO₃)]_n (2), [Cu₂(H₂L)₄(SO₄)₂]·11H₂O (3), and {[Ag(H₂L′)]BF₄}_n (4), the bipyrazoles act as bridging ligands to connect two metal atoms. Complexes 2 and 4 exhibit 1-D polymeric structures, while 1 and 3 are discrete molecules with a rectangular dimer or tetragonal prismatic shapes, respectively. Two different conformations, namely cis and trans, have been observed for these bipyrazolyl ligands.     

锌、镉配位聚合物的合成、晶体结构及荧光性质

通过水热法合成了2个金属-有机配位聚合物[Zn（boba）（bix）]_n=（1）和[Cd（L1）（L2）]_2n=·nH₂O（2）（H₂boba=4,4’-（丁烷-1,2-二氧基）-二苯甲酸,bix=1,4-双（咪唑基-1-基）苯,H₂L1=4-（羧基甲氧基）苯甲酸,L2=2-（4-羟基）-1H-咪唑并[4,5-f][1,10]菲咯啉）。并对其进行了元素分析、红外光谱、热重和X-射线单晶衍射测定。配合物1为二维网状结构,配合物2为一维双链结构。此外,还研究了它们的荧光性质。     

Three 2D mixed-ligand Co(II) coordination polymers containing flexible bis(benzimidazole) ligands with different spacers

Three new Co(II) coordination polymers, [Co(L1)(bpdc)] _n (1), [Co(L2)(ndc)(H₂O)·2H₂O] _n (2) and [Co(L3)(ndc)(H₂O)·H₂O] _n (3) (L1 = 1,2-bis(5,6-dimethylbenzimidazole)ethane, L2 = 1,3-bis(5,6-dimethylbenzimidazole)propane, L3 = 1,4-bis(5,6-dimethylbenzimidazole)butane, H₂bpdc = 4,4′-biphenyldicarboxylic acid, H₂ndc = 2,6-naphthalenedicarboxylic acid) have been synthesized under hydrothermal conditions and structurally characterized by X-ray crystallography. All three complexes feature (4,4) networks that extend into 3D supramolecular frameworks via hydrogen bonding interactions. The luminescence properties and catalytic activities of these complexes with respect to the degradation of methyl orange in a Fenton-like process have been investigated.     

Syntheses and characterization of four coordination compounds derived from 10,11,12,13-tetrahydro-4,5,9,14-tetraaza-benzo[b]triphenylene and benzene-dicarboxylic acids

[Co₂(TTBT)₄(1,2-BDC)₂] _n ?·?4nH₂O (1), [Pb₂(TTBT)₂(1,3-BDC)₂] _n ?·?nTTBT?·?2nH₂O (2), [Fe(TTBT)(1,4-BDC)(H₂O)] _n (3), and [Zn(TTBT)(1,4-BDC)(H₂O)] _n (4) have been hydrothermally synthesized by self-assembly of TTBT (TTBT?=?10,11,12,13-tetrahydro-4,5,9,14-tetraaza-benzo[b]triphenylene), benzene-dicarboxylic acid ligands 1,2-H₂BDC, 1,3-H₂BDC or 1,4-H₂BDC (1,2-H₂BDC?=?1,2-benzenedicarboxylic acid, 1,3-H₂BDC?=?1,3-benzenedicarboxylic acid, 1,4-H₂BDC?=?1,4-benzenedicarboxylic acid), and various metal salts. Compound 1 has dinuclear cluster units, four dimeric Co₂ units connected to form a 32-membered ring via weak offset π–π interactions, which are further stacked via strong π–π interactions to form a 3-D supramolecular framework. Complex 2 contains 2-D layers with rhombohedral grids, which are connected to a 3-D structure by π–π interactions. 3 and 4 feature 1-D infinite chains, which are further extended by strong π–π interactions and O–H···O hydrogen bonds resulting in 3-D supramolecular architectures. The photoluminescent properties of 2 and 4 have also been investigated.