Synthesis and Characterization of Metal Complexes of two Novel Pyridine‐Derived Macrocyclic Ligands Bearing o‐ and p‐Nitrobenzyl Pendant Groups

The pendant‐armed ligands L¹ and L² were synthesized by N‐alkylation of the two secondary aminic groups of the oxaazamacrocyclic precursor L with o‐nitrobenzylbromide (L¹) or p‐nitrobenzylbromide (L²). Metal complexes of L¹ and L² have been synthesized and characterized by microanalysis, MS‐FAB, conductivity measurements, IR, UV‐Vis, ¹H and ¹³C NMR spectroscopy and magnetic studies. Crystal structures of ligands L¹ and L², as well as complexes [CdL¹(NO₃)₂]·2CH₃CN and [Ag₂Br(L²)₂](ClO₄)·2CH₃CN have been determined by single crystal X‐ray crystallography.     

Thermochromic Luminescent Nest‐Like Silver Thiolate Cluster

A novel discrete open high‐nuclearity nest‐like silver thiolate cluster complex, [Ag₃₃S₃(StBu)₁₆(CF₃COO)₉(NO₃)(CH₃CN)₂](NO₃) ( 1 ), has been isolated with nitrate and S^2? anions acting as structure‐directing templates. Its similar nest‐like structure has been assembled into an extended layer [Ag₃₁S₃(StBu)₁₆(NO₃)₉]_n ( 2 ) by adjustment of auxiliary ligand. More interestingly, both complexes exhibit temperature‐dependent luminescence of high sensitivity with a large fluorescence enhancement (12‐fold for 1 , 21‐fold for 2 ), which can be easily recognized by the naked‐eye (dramatic red‐shift Δ=104 nm for 1 , larger Δ=113 nm for 2 at 77 K compared to those at 298 K). The correlation between luminescent thermochromism and temperature‐dependent variation of the coordination modes of template NO₃^? anion, Ag???S and Ag???Ag distances are also elucidated through variable‐temperature single‐crystal X‐ray crystal structure (VT‐SCXRD) analyses.     

四种新型柔性吡啶基配合物的合成、结构及配体构象与配合物结构的关系

合成了柔性配体3-吡啶甲酸-1,2-乙二酯(3-pyridinecarboxylic acid 1,2-ethanediyl ester,pcaede),并将其分别与Co盐和Hg盐进行组装,得到4个新配合物[Co(pcaede)2Cl2.2CH3CN.H2O]n(1),[Co(pcae-de)2Cl2.H2O]n(2),[Hg(pcaede)I2]n(3)和[Hg(pcaede)Br2]n(4),对其进行了元素分析、红外光谱及X射线单晶结构分析.配合物1和2为含有孔道的一维链状结构,配合物3是1D内消旋螺旋链,配合物4则是锯齿形1D链状结构.研究结果显示,孔道中填充的溶剂分子和平衡阴离子对配合物的组装有显著的影响.此外对4个配合物中配体的构象进行了理论计算.     

由柔性配体庚二酸组装的微孔稀土配位高聚物

合成了3种新的庚二酸(H₂pim)稀土配位高聚物[Nd(Hpim)(pim)(H₂O)]_n·2nH₂O(1),[RE₂(pim)₃(H₂O)]_n·nH₂O[RE=Er(2),RE=Ho(3)],并通过元素分析红外光谱和单晶X射线衍射技术确定了其组成和晶体结构.配合物1为具有微孔的三维网状结构.配合物2和3同构,通过两种类型的O-H…O氢键将由配位键构筑的二维骨架结构组装成三维超分子结构.在这3个配合物中,庚二酸配体在同一配合物的结构中均存在不同的构象,体现了柔性配体不同于刚性配体的配位特点.     

From Zero‐dimensional to One‐dimensional: Use of Metal‐­Ligand Affinity in Supramolecular Assembly

The self‐assembly of 4 ‐ MTPP [ 4 ‐ MTPP = 2‐(methylthio)‐4‐(pyridin‐4‐yl)pyrimidine] with Cu(NO₃)₂ and AgNO₃ was structurally investigated. For Cu(NO₃)₂, a discrete mononuclear Cu^II coordination compound, [Cu( 4 ‐ MTPP )₂(NO₃)₂] ( 1 ), resulted that is exclusively based on Cu–N coordination. For AgNO₃, a unique one‐dimensional double‐chain structure ( 2 ) was obtained with the Ag–N distances varying from 2.181(9) to 2.223(9) Å, and the average Ag–S distance being 2.98 Å. Compared to zero‐dimensional 1 , the extension to one‐dimensional 2 is considered to result from the specific affinity between Ag⁺ and the ligand 4 ‐ MTPP that is attributed to the strong coordinating tendency of silver for aromatic nitrogen and thioether sulfur atoms.     

Chair‐ and Boat‐Configurations of Silver(I) Complexes of Ditopic Ligand Involving Benzimidazolyl Substituents

The ditopic ligand 1, 2‐bis(benzimidazol‐1‐ylmethyl)benzene (L¹) as well as its silver(I) complexes [Ag₂L¹₂(CF₃CO₂)₂] ( 1 ) and [Ag₂L¹₂](CF₃SO₃)₂ · (L¹) · 2H₂O · 0.5C₂H₅OH ( 2 ) were prepared and structures characterized by X‐ray crystallography. The Ag^I atoms in 1 are trigonally coordinated by two N_BIm atoms from the arms of L¹ and by one O atom of the anion CF₃CO₂^—, while those in 2 are only linearly ligated by N_BIm. Different silver salts of CF₃CO₂^— and CF₃SO₃^— lead to different configurations of the dimeric unit [Ag₂L¹₂]²⁺: chair‐form in ( 1 ) but boat‐form in ( 2 ). The discrete molecules in both 1 and 2 are assembled into network structures through face‐to‐face π · · · π stacking and edge‐to‐face C—H · · · π interactions in the crystalline state, as well as N—H · · · O and C—H · · · O hydrogen bonds. Solution ¹H NMR studies showed the formation of one sole species in solution or a rapid equilibrium was established on the NMR time scale at room temperature.     

Synthesis,Characterization and Crystal Structure of the Dimeric Silver(I) Complex containing 4‐Amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione

The reaction of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT, 1 ) with AgNO₃ and triphenylphosphane in a molar ratio 1:1:2 in ethanol led to the dimeric complex {[Ag(AMTT)(PPh₃)₂]NO₃}₂·4EtOH ( 2 ). 2 was characterized by elemental analyses, IR, ³¹P NMR spectroscopy as well as single crystal X‐ray diffraction. Crystal data for 2 at ?80 °C: space group with a = 1265.5(2), b = 1300.9(2), c = 1509.5(2) pm, α = 83.77(2)°, β = 79.22(2)°, γ = 62.89(2)°, Z = 2, R₁ = 0.0330.     

Synthesis,X‐ray Studies,and Catalytic Efficacy of a Novel Iron Complex Containing an N,O‐Type Bidentate Thiazoline Ligand

The reactions of FeCl₃ · 6H₂O and 2‐(2′‐hydroxyphenyl)‐2‐thiazoline as a bidentate O‐N donor thiazoline ligand (thoz) afford a five‐coordinate Fe^III complex [Fe(thoz)₂Cl] with a distorted square pyramidal configuration. Complex [Fe(thoz)₂Cl] was isolated as air‐stable crystalline solids and fully characterized, including by single‐crystal X‐ray structure analysis. Complex [Fe(thoz)₂Cl] shows very efficient reactivity in the oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide (UHP) as the oxidant at room temperature in air.     

Synthesis,Characterization and Crystal Structure of a Silver(I) Complex containing AMTT (AMTT = 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione)

The reaction of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione with AgNO₃ in methanol led to the complex [Ag(ATT)₂]NO₃ ( 2 ). 2 was characterized by elemental analyses, IR, ¹HNMR and Raman spectroscopy as well as single‐crystal X‐ray diffraction. Crystal data for 2 at ?70 °C: space group P2₁/n with a = 1356.7(12), b = 770.4(7), c = 1475.2(12) pm, β = 111.730(15)°, Z = 4, R₁ = 0.0402.     

Cadmium(II) Complexes with Mixed cis‐Epoxysuccinate and 2,2′‐Bipyridyl‐Like Ligands: Syntheses,Crystal Structures,and Luminescent Properties

Two new Cd^II complexes, [Cd( ces )(phen)]_∞ ( 1 ) and {[Cd( ces )(bpy)(H₂O)](H₂O)}₂ ( 2 ), were prepared by slow solvent evaporation methods from mixtures of cis‐epoxysuccinic acid and Cd(ClO₄)₂ · 6H₂O in the presence of phen or bpy co‐ligand ( ces = cis‐epoxysuccinate, phen = 1,10‐phenanthroline, and bpy = 2,2′‐bipyridine). Single‐crystal X‐ray diffraction analyses show that complex 1 has a one‐dimensional (1D) helical chain that is further assembled into a two‐dimensional (2D) sheet, and then an overall three‐dimensional (3D) network by the interchain C–H ··· O hydrogen bonds. Complex 2 features a dinuclear structure, which is further interlinked into a 3D supramolecular network by the co‐effects of intermolecular C–H ··· O and C–H ··· π hydrogen bonds as well as π ··· π stacking interactions. The structural differences between 1 and 2 are attributable to the intervention of different 2,2′‐bipyridyl‐like co‐ligands. Moreover, 1 and 2 exhibit intense solid‐state luminescence at room temperature, which mainly originates from the intraligand π→π* transitions of aromatic co‐ligands.     

Luminescent Property of a Supramolecular Silver(I)‐Thiolate Complex Based on Secondary Ag‐S Interactions and Hydrogen Bonds

The supramolecular silver(I)‐thiolate complex [Ag(μ₂‐SC₄N₂H₄)₂(SCN)]_n has been prepared from the reaction of AgSCN and pyrimidine‐2‐thiol in DMF. X‐ray diffraction analysis shows that the supramolecular structure exhibits one‐dimensional chain through the secondary Ag‐S interactions and the chains are further linked by strong hydrogen bonds to form a three dimensional network. The luminescence effect from the silver‐centered state of S→Ag LMCT in solid state is different from that in solution due to the secondary Ag‐S interactions.     

The Crystal Structure of Solvent‐Free Silver Dodecachloro‐closo‐dodecaborate Ag2[B12Cl12] from Aqueous Solution

Colourless octahedral single crystals of solvent‐free Ag₂[B₁₂Cl₁₂] (cubic, Pa3¯; a = 1238.32(7) pm, Z = 4) are obtained by the metathesis reaction of Cs₂[B₁₂Cl₁₂] with an aqueous solution of silver nitrate (AgNO₃) and recrystallization of the crude product from water. The crystal structure is best described as a distorted anti‐CaF₂‐type arrangement in which the quasi‐icosahedral [B₁₂Cl₁₂]^2— anions (d(B—B) = d(B—Cl) = 177—180 pm) are arranged in a cubic closest‐packed fashion. The tetrahedral interstices are filled with Ag⁺ cations which are strongly displaced from their ideal positions. Thereby each silver atom gets coordinated by six chlorine atoms from the edges of three [B₁₂Cl₁₂]^2— anions providing a distorted octahedral coordination sphere to the Ag⁺ cations (d(Ag—Cl) = 283—285 pm, CN = 6).     

A Luminescent Silver(I) Metal‐Organic Framework with New (4,6)‐Connected Topology Based on Mixed Tetrachlorotereph­thalate and 2,2′‐Bipyridine Ligands

A silver(I) coordination polymer with mixed 2,3,5,6‐tetrachloro‐1,4‐benzenedicarboxylate (BDC‐Cl₄) and 2,2′‐bipyridine (2,2′‐bpy) ligands, [Ag₂(BDC‐Cl₄)(2,2′‐bpy)]_n ( 1 ), was synthesized and structurally characterized. Compound 1 features a robust three‐dimensional (3D) network, exhibiting a new (4,6)‐connected net with the Schläfli symbol of (3² · 4² · 5 · 6)₂(3² · 4² · 5² · 8⁷ · 9 · 10). The photoluminescence properties of 1 were investigated in the solid state at room temperature.     

N´-乙基-N-哌嗪基二硫代氨基甲酸钴(Ⅲ)配合物Co(S2CNC4H8NC2H5)3·3H2O的合成、表征及晶体结构

合成了标题化合物Co(S₂CNC₄H₈NC₂H₅)₃·3H₂O,得到黑色四棱柱状晶体。晶体属三方晶系, 空间群为R-3, 晶胞参数a=1.37700(19), b=1.37700(19), c=3.0090(6) nm, γ=120°, M_r=680.98, V= 4.9411(14) nm³, Z=6, D_c=1.373 g/cm³, F(000)=2160, R = 0.0510 和 wR = 0.1436。中心Co原子分别与来自三个N´-乙基-N-哌嗪基二硫代氨基甲酸的六个硫原子配位形成略微扭曲的八面体构型。六个Co-S键的键长范围在0.22682(13)~0.22703(14) nm, 热分析表明标题化合物在799.97°C完全分解。     

Construction of Four Coordination Polymers based on 2‐[4‐(Pyridine‐4‐yl)phenyl]‐1H‐imidazole‐4,5‐dicarboxylic Acid

The imidazole‐based dicarboxylate ligand 2‐(4‐(pyridin‐4‐yl)phenyl)‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃PyPhIDC), was synthesized and its coordination chemistry was studied. Solvothermal reactions of Ca^II, Mn^II, Co^II, and Ni^II ions with H₃PyPhIDC produced four coordination polymers, [Ca(μ₃‐HPyPhIDC)(H₂O)₂]_n ( 1 ), {[M₃(μ₂‐H₂PyPhIDC)₂(μ₃‐HPyPhIDC)₂₆(H₂O)₂] · 6H₂O}_n [M = Mn ( 2 ), Co ( 3 )], and {[Ni(μ₃‐HPyPhIDC)(H₂O)] · H₂O}_n ( 4 ). Compounds 1 – 4 were analyzed by IR spectroscopy, elemental analyses, and single‐crystal and powder X‐ray diffraction. Compound 1 displays a one‐dimensional (1D) infinite chain. Compounds 2 and 3 are of similar structure, showing 2D network structures with a (4,4) topology based on trinuclear clusters. Compound 4 has another type of 2D network structure with a 3‐connected (4.8²) topology. The results revealed that the structural diversity is attributed to the coordination numbers and geometries of metal ions as well as the coordination modes and conformations of H₃PyPhIDC. Moreover, the thermogravimetric analyses of all the compounds as well as luminescence properties of the H₃PyPhIDC ligand and compound 1 were also studied.     

Synthesis and Crystal Structure of 1,6-Bis(N,N-diethylthiocarbamoylimino)1,6-diphenyl-2.5-dithiahexane,its Dimeric AgI Complex [Ag2(C26H34N4S4)2](ClO4)2 · C7H8, and its Tetrameric μ-Tetrabromo AgI Complex [Ag4(C26H34N4S4)2Br4]

Synthesis and crystal structure of 1,6-Bis-(N,N-diethylaminothiocarbamoylimino)-1,6-diphenyl-2,5-dithiahexane are reported as well as those of its dimeric Ag^I complex (as monotoluene adduct of the diperchlorate) and its tetrameric μ-tetrabromo Ag^I complex.     

Syntheses,Crystal Structures,and Cytotoxicity Evaluation of two Chain‐like and Diamond‐like Silver(I) Complexes

Two coordination polymers [Ag(dach)]_n(NO₃)_n ( 1 ) and [Ag(teda)(F₃CSO₃)]_n ( 2 ) (dach = 1, 2‐diaminocyclohexane, teda = 1, 4‐diazabicyclo[2.2.2]octane) have been synthesized and characterized by X‐ray single crystal analysis and cytotoxicity investigation. Compound 1 has a one‐dimensional chain‐like structure which is extended by ligand unsupported Ag···Ag interactions, hydrophobic interaction and hydrogen bonds into a three‐dimensional supramolecular array while compound 2 shows three‐dimensional diamond‐like framework constructed by coordination bonds. The high cytotoxities of these two compounds imply that they are potential candidates for antitumor agents.     

Synthesis,Structure and Magnetic Properties of 1‐D Silver(I) Complexes with Benzoic Acids Bearing Ortho‐Imino Nitroxide and Para‐Nitronyl Nitroxide Radical Ligands

Two new 1‐D silver( I ) complexes, [Ag( I )1.5(IM‐oBA)(NO₃)0.5] ( 1 ) and [Ag( I )(NIT‐pBA)] ( 2 ), (IM‐oBAH = 2‐(2‐carboxyphenyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazol‐1‐yloxyl, NIT‐pBAH = 2‐(4‐carboxyphenyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐3‐oxido‐H‐imidazol‐3‐ium‐1‐yloxyl) have been prepared and structurally characterized. Complexes 1 and 2 crystallized in the monoclinic space groups of C2/c and P2₁/c, respectively. In complex 1 , the structure consists of trinuclear Ag(I) atoms with different linkages of IM‐oBA and nitrates. The trinuclear Ag(I) atoms are further coordinated to the neighbor IM‐oBA radicals via self‐assembly of the nitrogen atom of imine moiety and extended into formation of a polymeric chain. Complex 2 is constructed from a bis(carboxylato‐O,O')‐bridged centrosymmetric dimeric subunit and extended into a polymeric chain through self‐assembly coordination between metal ions and nitroxide groups of NIT‐pBA radicals. Temperature dependence of magnetic susceptibility measurements showed a weak ferromagnetic coupling between nitroxide radicals in 1 and 2 with J = 5.62 for 1 and 6.62 cm^?1 for 2 , respectively.     

Syntheses,Characterization and X‐Ray Structures of the first Copper(I) and Silver(I) Complexes with ATT (ATT = 6‐Aza‐2‐thiothymine)

The reaction of copper(I) chloride with 6‐aza‐2‐thiothymine (ATT, 1 ) and triphenylphosphane in methanol/chloroform gives [(ATT)CuCl(PPh₃)] ( 2 ) as a neutral complex. [(ATT)Ag(NO₃)(PPh₃)₂]·MeOH ( 3 ) can be obtained by the reaction of 1 with silver(I) nitrate and triphenylphosphane in methanol/chloroform in excellent yields and the single crystals of 3 can be obtained from acetonitril solution. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at —80 °C: space group I2/a with a = 1859.3(1), b = 1143.2(1), c = 2208.2(1) pm, β = 104.84(1)°, Z = 8, R₁ = 0.0355 and for 3 at —80 °C: space group P2₁/c with a = 1344.1(1), b = 1553.6(1), c = 1977, 3(3) pm, β = 105.26(1)°, Z = 4, R₁ = 0.0436.