具有生物活性的1,4-二氢吡啶衍生物的水热法合成及结构表征

1,4-二氢吡啶衍生物具有很好的生理活性。在医学上用作心血管疾病的防治保健药物,不仅能治疗肠胃疾病、雷诺氏病、脂肪肝、中毒性肝炎,也有抗衰老、防早熟等作用,还可以用作治疗肺动脉高压和癫痫病的辅助药物[1-2]。近年又发现1,4-二氢吡啶衍生物不但是一类高效的钙拮抗剂,亦是一种绿色饲料添加剂。它的合成通常采用文献报道的Hantzsch法合成[3],即将干燥氨气通入乙酰乙酸乙酯与醛的混合溶液中。该反应时间长、操作复杂,且氨气易对环境造成污染。正因为此,越来越多的化学家和药物学家将有机合成的研究重点放在对环境无污染的绿色合成上。如…     

Hydrothermal synthesis and novel two-dimensional architecture with fluorescent properties constructed using 2-bromo-1,4-benzenedicarboxylate

A novel two-dimensional complex, [Cu(bbdc)(phen)]·(H₂O)(bbdc = 2-bromo-1,4-benzenedicarboxylate dianion; phen = 1,10-phenanthroline), has been synthesized and structurally characterized by single crystal X-ray analysis. The crystal structure consists of infinite chains of [Cu₂( ₄-bbdc)]²⁺ units connected by bis-monodentate bbdc ligands, the coordination mode of which [ ₄-bbdc] is very rare in the phenyldicarboxylate complexes. The substituent group of bbdc is believed to be the growth key of this coordination network.     

Hydrothermal synthesis and crystal structure of two luminescent three-dimensional supramolecular complexes generated from mixed ligands

Two 3D metal-organic supramolecular complexes [Zn₂(btec)(2, 2′-bpy)₂(H₂O)₂] (1), [Cd₂(dpa)₂(phen)₂(H₂O)₂] (2) have been prepared by hydrothermal reaction and characterized by IR and single-crystal X-ray diffraction analysis. The 3D architectures of 1 and 2 both possess rectangular cavities. Furthermore, compounds 1 and 2 both show intense photoluminescent properties at room temperature.     

Hydrothermal synthesis, crystal structure, and photoluminescence of novel lanthanide metal organic frameworks constructed from 1,4-benzene-dicarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid as ligands

Abstract  

By using 1,4-benzene-dicarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid as mixed-linkers, three novel 3D lanthanide coordination polymers, [Ln(BDC)_0.5(BTEC)_0.5(H₂O)] (Ln = Eu (1) and Gd (2)) and [Tb(BDC)_0.5(BTEC)_0.5(H₂O)] (3) (H₂BDC = 1,4-benzene-dicarboxylic acid, H₄BTEC = 1,2,4,5-benzenetetracarboxylic acid) were synthesized via hydrothermal reaction. The X-ray single crystal analyses reveal that the three coordination polymers present two types of different crystal cell parameters and hereby exhibited two kinds of different metal–organic frameworks, although they have the similar chemical formula [Ln(BDC)_0.5(BTEC)_0.5(H₂O)]. Of these complexes, complexes 1 and 2 are isomorphous, crystallizing in monoclinic, space group P2₁/n. While 3 is a 3D eight-coordinated terbium complex with triclinic crystal system and P-1 space group. The occurrence of the different structures of these complexes under the similar preparation method may be related to the lanthanide contraction effect. Additional, the thermogravimetric analyses and photoluminescent properties for complexes 1 and 3 were discussed in detail.     

Hydrothermal synthesis, crystal structure and luminescence of four novel metal-organic frameworks

Using the principle of crystal engineering, four novel metal-organic coordination polymers, {[Cd₁(nic)2(H₂O)]2[Cd₂(nic)2(H₂O)2]}_n (1), [Cd₂(fma)2(phen)2]_n (2), [Cd(fma)(bipy)(H₂O)]_n (3) and [Zn(mal)(bipy)·3H₂O]_n (4) (nic=nicotinate, fma=fumarate, mal=malate, phen=phenanthroline, bipy=2,2′-bipyridine) have been synthesized by hydrothermal reaction of M(CH₃COO)2·2H₂O (M=Zn, Cd) with nicotinic acid, fumaric acid and cooperative L (L=phen, bipy), respectively. X-ray analysis reveals that complex 1 possesses an unprecedented two-dimensional topology structure constructed from three-ply-like layers, complex 2 is an infinite 2D undulating network, complex 3 is a 1D zigzag chain and complex 4 belongs to a 1D chain. The results indicate a transformation of fumarate into malate during the course of hydrothermal treatment of complex 4. The photophysical properties have been investigated with luminescent excitation and emission spectra.     

Three metal complexes based on tetrazolyl ligands: Hydrothermal syntheses,crystal structures,and fluorescence properties

Three new complexes based on 1-tetrazole-4-imidazole-benzene (Tibz), namely, [Cd(Tibz)₂(H₂O)₂] _n (I), [Mn(Tibz)₂(H₂O)₄] · 2H₂O (II) and [Co(Tibz)₂(H₂O)₄] · 2H₂O (III) have been synthesized through hydrothermal method and structurally characterized by element analyses, IR spectroscopy and single-crystal X-ray diffraction analyses (CIF files CCDC nos. 1443867 (I), 1443868 (II), 1443869 (III)). Single-crystal X-ray diffraction reveals that complex I is a 1D double-chain architecture, II and III are both mononuclear complexes. The results of single-crystal X-ray diffraction analyses indicate that the hydrogen bond and π··· π stacking exist in the complexes, which make great contribution to the stabilities of complexes I–III. The fluorescent properties of these complexes have also been studied in the solid state at room temperature.     

Hydrothermal synthesis, crystal structures, and properties of two Co(II) complexes based on 4-bromoisophthalic acid and N-donor ligands

Two new Co(II) complexes, [Co₂(H₂O)(Bipy)₂(Bript)₂] _n (I) and [Co(H₂O)(Phen)(Bript)] · H₂O (II), where H₂Bript = 4-bromoisophthalic acid, Bipy = 2,2??-bipyridine, and Phen = 1,10-phenanthroline, have been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Complex I has binuclear units in which two Co²⁺ ions are bridged by two carboxylate groups and a coordinaiod-water molecule, and the binuclear units are connected by Bript to generate a 1D helical chain. These 1D helical chains are further linked by ????? stacking interactions to form a 3D supramolecular network, while complex II has a 2D layer motif. In I and II, there exists extensive hydrogen bonding interactions. The thermal behavior of the two corresponding complexes have briefly been investigated.     

Hydrothermal synthesis,structure, and photoluminescence of four complexes based on 1H-imidazole-4,5-dicarboxylate or 1H-imidazole-2-carboxylate ligands

Four complexes, [Ag₄(bipy)₂(Himdc)₂(H₂O)₂] _n (1), [Ag(H₂imdc)] _n (2), [K(H₃imdc)(H₂imdc)(H₂O)₂] _n (3), and [Cu(Himc)₂] (4) (H₃imdc?=?1H-imidazole-4,5-dicarboxylic acid, H₂imc?=?1H-imidazole-2-carboxylic acid, and bipy?=?4,4′-bipyridine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis and elemental analysis. The obtained complexes exhibit different coordination structures; 1 contains a 2-D supramolecular layer based on two chains arraying uniformly in an ABAB manner. Compound 2 displays sawtooth-shaped 1-D chains extending to 2-D layers via hydrogen bond interactions. Compound 3 possesses a 3-D framework structure based on a 1-D chain via hydrogen bonding interactions. Compound 4 has a 3-D framework structure bearing a pcu-type topology. In addition, the photoluminescence for 1 has been investigated.     

Hydrothermal synthesis and crystal structure of a novel 2-D polymeric manganese (II) complex with mixed ligands

A novel polymeric complex, [Mn(phen)(pdc)]_∞ (phen=1,10-phenanthroline, H₂pdc=2,5-pyridinedicarboxylic acid) has been synthesized from the hydrothermal reaction system of H₂pdc, phen, MnO₂, and H₂O. [Mn(phen)(pdc)]_∞ is characteristic of an edge-sharing dinuclear Mn^II structure unit bridged by pdc, leading to a 2-D framework whose stacking is based on weak H-bond interaction. The temperature dependence of the magnetic susceptibility for [Mn(phen)(pdc)]_∞ indicates antiferromagnetic coupling [J = −2.76(4) cm⁻¹] between the adjacent paramagnetic Mn^II ions.     

Iron carbonyl cluster complexes with monophosphine ligands: synthesis,characterization, and crystal structure

Three new monophosphine-substituted iron carbonyl cluster complexes [(μ-PDT)Fe₂(CO)₅L] [(PDT = SCH₂CH₂CH₂S, L = P(CH₂Ph)₃, 1; P(C₆H₁₁)₃, 2; PPh₂(PhMe-p), 3)], which can be regarded as active site mimics for [FeFe]-hydrogenase, have been prepared in 40–70 % yields by reactions of the parent complex (μ-PDT)Fe₂(CO)₆ (A) with monophosphine ligands in the presence of the decarbonylating agent Me₃NO·2H₂O. All three complexes were characterized by elemental analysis and spectroscopic techniques, as well as by X-ray crystallography for complex 1. The IR spectra of the complexes reveal that the electron-donating abilities of the different monophosphine ligands follow the order PPh₂(PhMe-p) > P(C₆H₁₁)₃ > P(CH₂Ph)₃.     

新型高聚合度钨磷多金属氧酸盐超分子化合物的水热合成与晶体结构

首次报道了新型高聚合度钨磷多金属氧酸盐超分子化合物H16{[P4W14Na3 (H2O)7O58]2[Na4(H2O)13]2[P4W14Na2(H2O)2O56]}·24H2O的水热合成方法,用元素分析、IR和单晶X射线衍射等手段进行了表征．晶体属三斜晶系,P1空间群,a= 1．551 5(3)nm,b=1．866 4(4)an],c=2.224 9nm,α=105.10(3)°,β=96.74(3)°,γ= 95．23(3)°,V=6．127(2)nm3,Z=1,Mr=12 418.36,Dc=3．365 g·cm-3,μ=19．843 mm-1, F(000)=5 516,R=0．0 829,Rw=0．2 020．测定结果表明,标题化合物是由两个[P4W14Na3 (H2O)7O58]9-和一个[P4W14Na2(H2O)2O56]6-阴离子通过O-Na-O桥键合而成．     

Chiral diethylzinc complexes with diamine ligands: synthesis, crystal structure and enantioselective solvent-free alkylation

In search for conglomerates of stereochemically labile organometallic reagents, three new complexes between diethylzinc and diamine ligands have been synthesized and structurally characterized by single-crystal X-ray diffraction methods. Ligands include N,N,N′,N′-tetraethylethylenediamine (teeda), N-isopropyl-N,N′,N′-trimethylethylenediamine (itmeda), and (−)-sparteine (spa). Diethylzinc forms monomeric complexes, exhibiting a distorted tetrahedral coordination geometry around zinc in all three complexes, viz. [ZnEt₂(teeda)] (1), [ZnEt₂(itmeda)] (2), and [ZnEt₂(spa)] (3). Both 1 and 2 are stereochemically labile and exhibit chiral complexes, displaying different types of conformational chirality, but they form racemic crystals. By using the chiral crystals of 3 in a nucleophilic addition to benzaldehyde in the absence of solvent at low temperature, an increase in ee from approximately 8 to 10% was obtained (compared to the same reaction in solution). It thus seems feasible, not only to retain the enantioselectivity obtained in solution, but perhaps even to increase the ee by using solventless reactions.     

Hydrothermal synthesis,crystal structure,and properties of a novel magnesium phosphonate with a 1D chain structure

A novel 1D chain magnesium phosphonate with a 1D channel system along the c-axis, [Mg(H₄L)(H₂O)₃]_n (1) (H₄L^2-=HN(CH₂PO₃H)₃)^2-, has been synthesized under hydrothermal condition using triphosphonate ligand. The MgO₆ polyhedra and NC₃ planes are connected by phosphonate groups to form a 1D chain. The chains are interlinked by hydrogen bonds into 2D layers. Adjacent layers are further linked via hydrogen bonds to build a 3D network structure. The luminescent property of complex 1 has been also studied. For the complex 1, a blue fluorescent emission band with a maximum peak at 460 nm was observed.     

Hydrothermal synthesis, crystal structure, and luminescence of a novel tetranuclear zinc(ii) complex

A new tetranuclear zinc(II) complex [Zn₄(tmphen)₄(tbip)₄(H₂O)₄] (1, tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline, H₂tbip = 5-tert-butyl isophthalic acid) is hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, elemental analysis, and IR spectroscopy. In complex 1, four tbip^2? ligands act as bridges between four neighboring Zn atoms to form an unusual tetranuclear zinc cluster. The clusters are further connected by two types of O-H…O and C-H…O hydrogen bonds, generating a three-dimensional supramolecular structure. Meanwhile, π-π stacking interactions and C-H…π interactions further consolidate the three-dimensional supramolecular framework of 1. In addition, the luminescence measurements reveal that complex 1 exhibits strong fluorescent emissions in the solid state at room temperature.     

Copper(II) complexes of tridentate SNO ligands: synthesis,characterization and crystal structure

A new series of binary copper(II) complexes, [Cu(L)₂] (2) [where L is a monobasic tridentate methylthioazophenolate having NSO donor sets], has been synthesized. The reddish brown colored complexes have been characterized by elemental analyses, spectroscopic and other physico-chemical tools. The detailed structure analysis of one of the complexes, [Cu(1a)₂] (2a), by single-crystal X-ray crystallography shows that thioether-S donor center participates in coordination with the copper(II) ion with a weak interaction with long Cu–S(thioether) bond distances [2.956(2) Å and 2.925(2) Å]. Electrochemical study of the complexes in methanol using TBAP as supporting electrolyte shows that heterogeneous electron-transfer rate is low at the applied potential.     

A novel series of rhenium-bipyrimidine complexes: synthesis, crystal structure and electrochemical properties

Four novel rhenium complexes of formula [ReCl(4)(bpym)] (1), [ReBr(4)(bpym)] (2) PPh(4)[ReCl(4)(bpym)] (3) and NBu(4)[ReBr(4)(bpym)] (4) (bpym = 2,2'-bipyrimidine, PPh(4) = tetraphenylphosphonium cation and NBu(4) = tetrabutylammonium cation), have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. The structures of 1 and 2 consist of [ReX(4)(bpym)] molecules held together by van der Waals forces. In both complexes the Re(iv) central atom is surrounded by four halide anions and two nitrogen atoms of a bpym bidentate ligand in a distorted octahedral environment. The structures of 3 and 4 consist of [ReX(4)(bpym)](-) anions and PPh(4)(+) () or NBu(4)(+) (4) cations. The coordination sphere of the Re(iii) metal ion is the same as in 1 and 2, respectively. However, whereas the Re-X bonds are longer the Re-N bonds are shorter than in 1 and 2. This fact reveals that the bpym ligand forms a stronger bond with Re(iii) than with Re(iv) resulting in a stabilisation of the lower oxidation state. [ReX(4)(bpym)] complexes are easily reduced, chemically and electrochemically, to the corresponding [ReX(4)(bpym)](-) anions. A voltammetric study shows that the electron transference is a reversible process characterized by formal redox potentials of +0.19 V (1) and +0.32 V (2) vs. NHE, in acetonitrile as solvent.     

基于2，5-二溴对苯二甲酸配体的锰/钴配合物的合成、晶体结构及性质

将有机物2,5-二溴对苯二甲酸(H₂L₁)作为主配体,2,2′-联吡啶(L₂)、1,10-菲咯啉(L₃)分别作为辅配体,通过溶剂热法与一水硫酸锰、六水合硝酸钴分别反应得到配合物[Mn₂(L₁)₂(L₂)₂(H₂O)₂]_n (1)和[Co₂(L₁)₂(L₃)₂(H₂O)₂]_n(2)。通过单晶X射线衍射法、荧光光谱、热重分析等测试手段对这2种配合物进行分析研究。结果表明配合物1是由Mn²⁺配位连接L₁^2-与L₂形成无限延伸的二维网络状结构,各层在分子间氢键和π-π堆积作用...     

Hydrothermal synthesis, crystal structure and properties of Ni(II)-4f complexes based on 1H-benzimidazole-5,6-dicarboxylic acid

Nine novel heterometallic coordination polymers [Ln(2)Ni(Hbidc)(2)(SO(4))(2)(H(2)O)(8)](n) (Ln = Pr (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6), Ho (7), Er (8), Yb (9), H(3)bidc = 1H-benzimidazole-5,6-dicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, FT-IR, TG analysis and single crystal X-ray diffraction. X-ray analysis revealed that all complexes present almost identical three-dimensional (3D) structures with PtS-type topology. Complexes 1-7 are all isomorphous, and the structure variation of polymers 8 and 9 is induced by the lanthanide contraction effect. In additional, the luminescence properties of complexes 2, 3 and 5-7, and the magnetic properties of complexes 4 and 6-8 were investigated.     

基于2，5-二溴对苯二甲酸配体的锰/钴配合物的合成、晶体结构及性质

将有机物2,5-二溴对苯二甲酸(H₂L1)作为主配体,2,2′-联吡啶(L₂)、1,10-菲咯啉(L₃)分别作为辅配体,通过溶剂热法与一水硫酸锰、六水合硝酸钴分别反应得到配合物[Mn₂(L₁)₂(L₂)₂(H₂O)₂]_n (1)和[CO₂(L₁)₂(L₃)₂(H₂O)₂]_n (2)。通过单晶 X射线衍射法、荧光光谱、热重分析等测试手段对这 2种配合物进行分析研究。结果表明配合物 1是由 Mn²⁺配位连接 L₁^2-与 L₂形成无限延伸的二维网络状结构,各层在分子间氢键和π-π堆积作用下形成了三维网络状结构。配合物2是由CO²⁺配位连接L₁^2-和L₃形成的无限延伸的二维网络状结构,各层在分子间氢键和π-π堆积作用下形成三维网络状结构。且这2种配合物均具有良好的荧光性和热稳定性,配合物1和2的最大发射波长分别为355和365 nm。     

Synthesis,characterization, crystal structure,and antimicrobial studies of novel thiourea derivative ligands and their platinum complexes

N,N-Di-R-N′-(4-chlorobenzoyl)thiourea (Di-R: diethyl, di-n-propyl, di-n-butyl and diphenyl) ligands (HL^1–4) and their Pt(II) complexes (cis-[Pt(L^1–4-S,O)₂]) have been synthesized and structurally characterized by elemental analyses, FT-IR and NMR spectroscopy. HL² ligand and cis-[Pt(L⁴-S,O)₂] metal complex have been also characterized by a single-crystal X-ray diffraction study. HL², C₁₄H₁₉ClN₂OS, crystallizes in the monoclinic space group P2₁/n (no. 14), with Z = 4, and unit cell parameters, a = 11.1405(16) Å, b = 9.7015(12) Å, c = 14.790(2) Å, β = 106.547(7)°. The cis-[Pt(L⁴-S,O)₂], C₄₀H₂₈Cl₂N₄O₂PtS₂: triclinic, space group P-1 (no. 2), a = 8.9919(3) Å, b = 14.7159(6) Å, c = 15.7954(6) Å, α = 113.9317(18)°, β = 97.4490(18)°, and γ = 105.0492(16)°. Single crystal analysis of complex, cis-[Pt(L^1–4-S,O)₂], revealed that a square planar coordination geometry is formed around the platinum atom by two sulfur and two oxygen atoms of the related ligands, which are in a cis configuration. In addition, the thiourea derivative ligands and their complexes were evaluated for both their in-vitro antibacterial and antifungal activity. The results have been reported, explained, and compared with fluconazole and ampicillin, used as reference drugs.