Rapid Thermolysis Studies of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O and Cd（CHZ）2（TNR）（H2O）

T-jump/FT-IR spectroscopy was used to study the rapid thermal decomposition activity of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O and Cd（CHZ）2（TNR）（H2O） under 0.1 MPa Ar atmosphere. The results show that the main gaseous products of [Pb2（TNR）2（CHZ）2（H2O）2]·4H2O are NH3, H2O and HONO, while CO and NO are the major gaseous products of flash pyrolysis of Cd（CHZ）2（TNR）（H2O）. Thus Cd（CHZ）2（TNR）（H2O） is not an eco-friendly and chemically compatible primary explosive. Both compounds liberate volatile metal carbonate, oxide and isocyanate compounds. The combustion temperature and products of the two compounds were calculated by Real code. The results of theoretical calculation show that the combustion temperature of [Pb2（TNR）2（CHZ）2（H2O）2].4H2O is higher than that of Cd（CHZ）2（TNR）（H2O）, there is no HNCO in the combus- tion products and the amount of NO is less than the experiment result from T-jump/FTIR.     

Synthesis and Structural Characterization of Cu（pic）2[CO（NH2）2]2 and （picH2）2[Cu（pic）2（SCN）2]

1 INTRODUCTION The picolinic acid (picH), also called pyridine- 2-carboxylic acid, has a broad spectrum of physio- logical effects on the activity functions of both ani- mal and plant organisms. It is attributed increasing interest due to its ability to …     

[（phen）2Mn2（μ—O）（μ—Ac）2（H2O2）]（ClO4）2·4H2O双核锰？…

MnAc3.2H2O在pH=4.0的HAc-NaAc缓冲溶液中和邻菲罗啉(phen)反应, 制得了双核锰(Ⅲ)合物[(phen)2Mn2(μ-O)(μ-Ac)2 (H2O)2](ClO4)2.H2O, 并进行了红外光谱表征. X射线单晶衍射表明, 该晶体属单斜晶系, 空间群P21/n, 晶胞参数: a=1.025 28(5) nm, b=1.792 75(9) nm, c=1.984 14(10) nm, β=94.843 0(10)°, V=3.634 0(3) nm3, Z=4, Dc=1.669 g.cm-3. 紫外可见光谱在480 nm处有一个吸收峰. 循环伏安实验说明, 此配合物在乙腈溶液中经历了一个半可逆的一电子氧化还原过程.     

配位化合物[Cd（hca）2（H2O）3]（H2O）2,[Cu（hca）2（phen）]的合成与表征

配合物1由醋酸镉和Nahca(对羟基肉桂酸钠)在水溶液中反应得到,配合物2由醋酸铜,Hhca和phen在水和乙醇混合溶液中反应得到.配合物1属正交晶系,Pbcn空间群.配合物2属单斜晶系,C2/c空间群.配合物1和2中配体中的羧酸根与金属离子都是螯合配位的,末端羟基没有参与配位.配合物1和2的结构中都包含了丰富的氢键.通过氢键作用,配合物1形成了三维网状超分子结构,配合物2形成了二维层状超分子结构.     

Synthesis and Crystal Structure of DinuclearCadmium Complex [Cd2（phen）4（fca）2]（ClO4）2-（H2O）2

1 INTRODUCTION During the search of molecule-based materials with interesting properties such as catalysis, cla- thration etc., much attention has been focused on the synthesis of one-, two- and three-dimensional extended solids involving cadmium[1], as its d10 configuration permits a wide variety of geometries and coordination numbers. Rigid bridged ligands such as carboxylate groups are frequently used to construct these materials. Therefore, the coordi- nation chemistry of Cd(Ⅱ) ca…     

Synthesis and Crystal Structure of （Et4N）2[Pd2（mp）2（mpH）2]

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ（Ｅｔ_４Ｎ）_２［Ｐｄ_２（ｍｐ）_２（ｍｐＨ）_２］ＳｈｉＪｉ－Ｃｈｅｎｇ；ＨｕａｎｇＸｉａｏ－Ｙｉｎｇ；ＷｅｎＴｉｎｇ－Ｂｉｎ；ＤｅｎｇＹｕ－Ｈｅｎｇ；ＣｈｅｎｇＣｈａｎｇ－Ｎｅｎｇ；Ｌｉ?..     

catena‐Poly[[silver(I)‐μ‐[9,10‐bis(1H‐benzimidazol‐1‐ylmethyl)anthracene]‐κ2N3:N3′] bis(nitrato‐κO)silver(I)]

Yellow needle‐shaped crystals of the title compound, {[Ag(C₃₀H₂₂N₄)][Ag(NO₃)₂]}_n, were obtained by the reaction of AgNO₃ and 9,10‐bis(benzimidazol‐1‐ylmethyl)anthracene (L) in a 2:1 ratio. The asymmetric unit consists of two Ag^I cations, one half L ligand and one nitrate anion. One Ag^I cation occupies a crystallographic inversion centre and links two N‐atom donors of two distinct L ligands to form an infinite one‐dimensional coordination polymer. The second Ag^I cation lies on a crystallographic twofold axis and is coordinated by two O‐atom donors of two nitrate anions to form an [Ag(NO₃)₂]⁻ counter‐ion. The polymeric chains are linked into a supramolecular framework via weak Ag...O [3.124 (5) Å] and Ag...π (2.982 Å) interactions (π is the centroid of an outer anthracene benzene ring). The π interactions contain two short Ag...C contacts [2.727 (6) and 2.765 (6) Å], which can be considered to define Ag–η²‐anthracene bonding interactions. In comparison with a previously reported binuclear Ag^I complex [Du, Hu, Zhang, Zeng & Bu (2008). CrystEngComm, 10 , 1866–1874], this new one‐dimensional coordination polymer was obtained by changing the metal–ligand ratio during the synthesis.     

Counter‐anion role in the formation of two supramolecular complexes: [Ag2(DPP)2](ClO4)2·CH3CN and [Ag2(DPP)2(NO3)2] {DPP is N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine}

The title compounds, bis{μ‐N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine‐κ²N¹:P}disilver bis(perchlorate) acetonitrile monosolvate, [Ag₂(C₁₈H₁₇N₂P)₂](ClO₄)₂·CH₃CN, (1), and bis{μ‐N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine‐κ²N¹:P}bis[(nitrato‐κ²O,O)silver], [Ag₂(C₁₈H₁₇N₂P)₂(NO₃)₂], (2), each contain disilver macrocyclic [Ag₂(C₁₈H₁₇N₂P)₂]²⁺ cations lying about inversion centres. The cations are constructed by two N‐[(diphenylphosphanyl)methyl]pyridin‐4‐amine (DPP) ligands linking two Ag⁺ cations in a head‐to‐tail fashion. In (1), the unique Ag⁺ cation has a near‐linear coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands. Two ClO₄⁻ anions doubly bridge two metallomacrocycles through Ag...O and N—H...O weak interactions to form a chain extending in the c direction. The half‐occupancy acetonitrile molecule lies with its methyl C atom on a twofold axis and makes a weak N...Ag contact. In (2), there are two independent [Ag(C₁₈H₁₇N₂P)]⁺ cations. The nitrate anions weakly chelate to each Ag⁺ cation, leading to each Ag⁺ cation having a distorted tetrahedral coordination geometry consisting of one pyridine N atom and one P atom from two different DPP ligands, and two chelating nitrate O atoms. Each dinuclear [Ag₂(C₁₈H₁₇N₂P)₂(NO₃)₂] molecule acts as a four‐node to bridge four adjacent equivalent molecules through N—H...O interactions, forming a two‐dimensional sheet parallel to the bc plane. Each sheet contains dinuclear molecules involving just Ag1 or Ag2 and these two types of sheet are stacked in an alternating fashion. The sheets containing Ag1 all lie near x = , , etc, while those containing Ag2 all lie near x = 0, 1, 2 etc. Thus, the two independent sheets are arranged in an alternating sequence at x = 0, , 1, etc. These two different supramolecular structures result from the different geometric conformations of the templating anions which direct the self‐assembly of the cations and anions.     

Synthesis,Characterization, and Photoluminescence Properties of Silver(I) Metal‐Organic Polymers with Nanochannels Based on 2‐Sulfoterephthalic Acid and Di(pyridin‐2‐yl)amine Ligands

Two new silver(I) 3D coordination polymers, namely [Ag₃(2‐stp)(dpa)]_n ( 1 ) and {[Ag₂(2‐stp)(H₂O)]?Hdpa}_n ( 2 ) (2‐NaH₂stp=sodium 2,5‐dicarboxysulfonate, dpa=di(pyridine‐2‐yl)amine) were synthesized. The complexes were characterized by elemental analysis, FT‐IR spectra, thermogravimetric analyses (TGA), and single‐crystal X‐ray diffraction. In complex 1 , three neighboring Ag ions are bridged by N‐ and O‐atom, forming a 3D coordination network. The molecular structure of 2 is cation? anion species, forming 3D host? guest supramolecular network with the [Hdpa]⁺ cations encapsulated in the nanochannels. The photoluminescence properties of the complexes were also investigated in the solid state at room temperature.     

The heterometallic cadmium–silver complex cis‐bis[dicyanidoargentato(I)‐κN]bis(5,5′‐dimethyl‐2,2′‐bipyridyl‐κ2N,N′)cadmium(II) monohydrate

In the title complex, [Ag₂Cd(CN)₄(C₁₂H₁₂N₂)₂]·H₂O or cis‐[Cd{Ag(CN)₂}₂(5,5′‐dmbpy)₂]·H₂O, where 5,5′‐dmbpy is 5,5′‐dimethyl‐2,2′‐bipyridyl, the asymmetric unit consists of a discrete neutral [Cd{Ag(CN)₂}₂(5,5′‐dmbpy)₂] unit and a solvent water molecule. The Cd^II cation is coordinated by two bidentate chelate 5,5′‐dmbpy ligands and two monodentate [Ag^I(CN)₂]⁻ anions, which are in a cis arrangement around the Cd^II cation, leading to an octahedral CdN₆ geometry. The overall structure is stabilized by a combination of intermolecular hydrogen bonding, and Ag^I...Ag^I and π–π interactions, forming a three‐dimensional supramolecular network.     

Anion‐directed Silver(I) Coordination Assemblies Based on 1‐(2‐Pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazolewith Diverse Supramolecular Networks and Dichromate Removal Capabilities

A series of silver(I) supramolecular complexes, namely, {[Ag(L²⁴)](NO₃)}_n ( 1 ), [Ag₂(L²⁴)(NO₂)₂]_n ( 2 ), and {[Ag_1.25(L²⁴)(DMF)](PF₆)_1.25}_n ( 3 ) were prepared by the reactions of 1‐(2‐pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazole (L²⁴) and silver(I) salts with different anions (AgNO₃, AgNO₂, AgPF₆). Single‐crystal X‐ray diffraction indicates that 1 – 3 display diverse supramolecular networks. The structure of dinuclear complex 1 is composed of a six‐membered Ag₂N₄ ring with the Ag ··· Ag distance of 4.4137(3) Å. In complex 2 , the adjacent Ag^I centers are interlinked by L²⁴ ligands into a 1D chain, the adjacent of which are further extended by the bridged nitrites to construct a 2D coordination architecture. Complex 3 shows a 3D (3,4)‐connected framework, which is generated by the linkage of L²⁴ ligands. All complexes were characterized by IR spectra, elemental analysis, and powder X‐ray diffraction. Notably, a structural comparison of the complexes demonstrates that their structures are predominated by the nature of anions. Additionally, 1 and 2 show efficient dichromate (Cr₂O₇^2–) capture in water system, which can be ascribed to the anion‐exchange.     

A two‐dimensional network formed by self‐associating silver(I) perchlorate with 3‐[4‐(2‐thienyl)‐2H‐cyclopenta[d]pyridazin‐1‐yl]benzonitrile

In the organometallic silver(I) supramolecular complex poly[[silver(I)‐μ₃‐3‐[4‐(2‐thienyl)‐2H‐cyclopenta[d]pyridazin‐1‐yl]benzonitrile] perchlorate methanol solvate], {[Ag(C₁₈H₁₁N₃S)](ClO₄)·CH₃OH}_n, there is only one type of Ag^I center, which lies in an {AgN₂Sπ} coordination environment. Two unsymmetric multidentate 3‐[4‐(2‐thienyl)‐2H‐cyclopenta[d]pyridazin‐1‐yl]benzonitrile (L) ligands link two Ag^I atoms through π–Ag^I interactions into an organometallic box‐like unit, from which two 3‐cyanobenzoyl arms stretch out in opposite directions and bind two Ag^I atoms from neighboring box‐like building blocks. This results in a novel two‐dimensional network extending in the crystallographic bc plane. These two‐dimensional sheets stack together along the crystallographic a axis to generate parallelogram‐like channels. The methanol solvent molecules and the perchlorate counter‐ions are located in the channels, where they are fixed by intermolecular hydrogen‐bonding interactions. This architecture may provide opportunities for host–guest chemistry, such as guest molecule loss and absorption or ion exchange. The new fulvene‐type multidentate ligand L is a good candidate for the preparation of Cp–Ag^I‐containing (Cp is cyclopentadienyl) organometallic coordination polymers or supramolecular complexes.     

Octahedral and Cyclic [Ag6] Cluster Cores Stabilized by {Ag3(Spz)3(N‐triphos)3} Motifs [HSpz = Pyrazine‐2‐thiolate,N‐triphos = Tris((diphenylphosphanyl)methyl)amine]: Ag···Ag Interactions

The complexes [Ag₁₂(Spz)₁₂(N‐triphos)₂][Ag₃(Spz)₃(N‐triphos)]₂ · (DMF)₆ ( 1 ) and [Ag₁₈(Spz)₁₂(N‐triphos)₄(CF₃CO₂)₆] ( 2 ) were synthesized and structurally characterized by X‐ray diffraction [HSpz = pyrazine‐2‐thiolate, N‐triphos = tris((diphenylphosphanyl)methyl)amine]. The central [Ag₆] ring with chair‐conformation in 1 and the ideally octahedral [Ag₆] cluster core in 2 are both stabilized by the tripodal building units of neutral [Ag₃(Spz)₃(N‐triphos)] compound. The Ag ··· Ag distances of the [Ag₆] moieties in 1 and 2 are 3.07 and 2.81 Å, respectively, exhibiting intermetallic interactions, which can enhance the stability of [Ag₆] conformations. In addition, the π ··· π interactions between parallel pyrazine rings could impose on the building and the Ag ··· Ag interactions of these Ag–S clusters.     

Syntheses and Structural Characterization of Four New Silver(I) Complexes with the N,N′(O)‐bidentate Bridging Ligands

Four new bridged silver(I) complexes, namely [Ag₂(μ₂‐teda)(μ₂‐fbc)₂] ( 1 ), [Ag₂(μ₂‐1,6‐dah)₂](bpdc) · 4H₂O ( 2 ), [Ag₂(μ₂‐2‐ap)(2‐ap)(bnb)] · 0.34H₂O ( 3 ), [Ag₂(μ₂‐pyc)₂(2‐apy)₂] · 0.5H₂O ( 4 ), have been synthesized and characterized by elemental analysis and crystallographic methods [fbc = 4‐fluorobenzoate, teda = triethylenediamine ( 1 ); bpdc = biphenyl‐4,4′‐dicarboxylate, 1,6‐dah = 1,6‐diaminohexane ( 2 ); bnb = 3,5‐binitrobenzoate, 2‐ap = 2‐aminopyrimidine ( 3 ); pyc = 3‐pyridinecarboxylate acid, 2‐apy = 2‐aminopyridine ( 4 )]. Complex 1 contains a 1D linear chain paralleling to the c‐axis, whereas in complex 2 silver(I) atoms were bridged by the 1,6‐dah ligand into a zigzag chain, further giving a 1D ribbon by weak Ag ··· Ag interactions. Complex 3 consists of a dinuclear silver(I) [Ag₂(μ₂‐2‐ap)(2‐ap)(bnb)] moiety and a lattice water molecule, forming a 3D network via a number of hydrogen‐bonding interactions such as N–H ··· O, N–H ··· N and C–H ··· O hydrogen bond and other weak interactions such Ag ··· Ag, Ag ··· N, N ··· O as well as O ··· O interaction. Similar to 3 , the asymmetric unit of 4 consists of one dinuclear silver(I) [Ag₂(μ₂‐pyc)₂(2‐apy)₂] moiety and half lattice water molecule, further generating a tetranuclear silver(I) {[Ag₂(μ₂‐pyc)₂(2‐apy)₂]₂ · H₂O} moiety. These moieties construct a 3D supramolecular network structure of 4 through N–H ··· O, O–H ··· O and C–H ··· O hydrogen bonds as well as other weak interactions such as Ag ··· O and N ··· O interactions.     

Chiral one‐ and two‐dimensional silver(I)–biotin coordination polymers

Reaction of biotin {C₁₀H₁₆N₂O₃S, HL; systematic name: 5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoic acid} with silver acetate and a few drops of aqueous ammonia leads to the deprotonation of the carboxylic acid group and the formation of a neutral chiral two‐dimensional polymer network, poly[[{μ₃‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}silver(I)] trihydrate], {[Ag(C₁₀H₁₅N₂O₃S)]·3H₂O}_n or {[Ag(L)]·3H₂O}_n, (I). Here, the Ag^I cations are pentacoordinate, coordinated by four biotin anions via two S atoms and a ureido O atom, and by two carboxylate O atoms of the same molecule. The reaction of biotin with silver salts of potentially coordinating anions, viz. nitrate and perchlorate, leads to the formation of the chiral one‐dimensional coordination polymers catena‐poly[[bis[nitratosilver(I)]‐bis{μ₃‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}] monohydrate], {[Ag₂(NO₃)₂(C₁₀H₁₆N₂O₃S)₂]·H₂O}_n or {[Ag₂(NO₃)₂(HL)₂]·H₂O}_n, (II), and catena‐poly[bis[perchloratosilver(I)]‐bis{μ₃‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}], [Ag₂(ClO₄)₂(C₁₀H₁₆N₂O₃S)₂]_n or [Ag₂(ClO₄)₂(HL)₂]_n, (III), respectively. In (II), the Ag^I cations are again pentacoordinated by three biotin molecules via two S atoms and a ureido O atom, and by two O atoms of a nitrate anion. In (I), (II) and (III), the Ag^I cations are bridged by an S atom and are coordinated by the ureido O atom and the O atoms of the anions. The reaction of biotin with silver salts of noncoordinating anions, viz. hexafluoridophosphate (PF₆⁻) and hexafluoridoantimonate (SbF₆⁻), gave the chiral double‐stranded helical structures catena‐poly[[silver(I)‐bis{μ₂‐5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}] hexafluoridophosphate], {[Ag(C₁₀H₁₆N₂O₃S)₂](PF₆)}_n or {[Ag(HL)₂](PF₆)}_n, (IV), and catena‐poly[[[{5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}silver(I)]‐μ₂‐{5‐[(3aS,4S,6aR)‐2‐oxohexahydro‐1H‐thieno[3,4‐d]imidazol‐4‐yl]pentanoato}] hexafluoridoantimonate], {[Ag(C₁₀H₁₆N₂O₃S)₂](SbF₆)}_n or {[Ag(HL)₂](SbF₆)}_n, (V), respectively. In (IV), the Ag^I cations have a tetrahedral coordination environment, coordinated by four biotin molecules via two S atoms, and by two carboxy O atoms of two different molecules. In (V), however, the Ag^I cations have a trigonal coordination environment, coordinated by three biotin molecules via two S atoms and one carboxy O atom. In (IV) and (V), neither the ureido O atom nor the F atoms of the anion are involved in coordination. Hence, the coordination environment of the Ag^I cations varies from AgS₂O trigonal to AgS₂O₂ tetrahedral to AgS₂O₃ square‐pyramidal. The conformation of the valeric acid side chain varies from extended to twisted and this, together with the various anions present, has an influence on the solid‐state structures of the resulting compounds. The various O—H...O and N—H...O hydrogen bonds present result in the formation of chiral two‐ and three‐dimensional networks, which are further stabilized by C—H...X (X = O, F, S) interactions, and by N—H...F interactions for (IV) and (V). Biotin itself has a twisted valeric acid side chain which is involved in an intramolecular C—H...S hydrogen bond. The tetrahydrothiophene ring has an envelope conformation with the S atom as the flap. It is displaced from the mean plane of the four C atoms (plane B) by 0.8789 (6) Å, towards the ureido ring (plane A). Planes A and B are inclined to one another by 58.89 (14)°. In the crystal, molecules are linked via O—H...O and N—H...O hydrogen bonds, enclosing R₂²(8) loops, forming zigzag chains propagating along [001]. These chains are linked via N—H...O hydrogen bonds, and C—H...S and C—H...O interactions forming a three‐dimensional network. The absolute configurations of biotin and complexes (I), (II), (IV) and (V) were confirmed crystallographically by resonant scattering.     

catena‐Poly­[[(di‐2‐pyridyl­amine)­silver(I)]‐μ‐nicotinato] and catena‐poly­[[(di‐2‐pyridyl­amine)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato]

In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐nico­tinato‐κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.