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Computational studies revealed that dirhodium tetrakis(1,2,2‐triarylcyclopropanecarboxylate) (Rh2(TPCP)4) catalysts adopt distinctive high symmetry orientations, which are dependent on the nature of the aryl substitution pattern. The parent catalyst, Rh2(TPCP)4, and those with a p‐substituent at the C1 aryl, such as Rh2(p‐BrTPCP)4 and Rh2(p‐PhTPCP)4, adopt a C2‐symmetric structure. Rh2(3,5‐di(p‐tBuC6H4)TPCP)4, 3,5‐disubstituted at the C1 aryl, adopts a D2‐symmetric structure, whereas catalysts with an o‐substituent at the C1 aryl, such as Rh2(o‐Cl‐5‐BrTPCP)4, adopt a C4‐symmetric structure. [ABSTRACT FROM AUTHOR]

The synthesis of four heteroleptic dinuclear Cu(I) complexes bearing tetraphosphine and diimine ligands was reported. Complexes 1–3 were successfully obtained through microwave synthesis while complex 4 was synthesized through traditionally stirring at room temperature. These complexes are listed as follows: [Cu2(Dpq)2(dppeda)](ClO4)2·1.5CH2Cl2 (1), [Cu2(neo)2(dppeda)](ClO4)2·1.3CH2Cl2·1.7C4H10O (2), [Cu2(batho)2(dppeda)](ClO4)2·C4H10O (3), and [Cu2(batho)2(dpppda)](ClO4)2·3CH2Cl2 (4) {(Dpq = pyrazino[2,3-f][1,10]phenanthroline, batho = 4,7-diphenyl-1,10-phenanthroline, neo = 2,9-dimethyl-1,10-phenanthroline, dppeda = N1,N1,N2,N2-tetrakis[(diphenylphosphino)methyl]-1,2-ethanediamine, and dpppda = N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamine}. Their crystal structures have been elucidated by X-ray crystallography and their photophysical properties have been investigated in detail. Photophysical studies and time domain density functional theory (TD-DFT) calculations show that the luminescence performance of these four complexes is ascribed to metal-to-ligand charge transfer (MLCT) mixed with ligand-to-ligand charge transfer (LLCT), and complex 2 shows green emission at 574 nm with the highest quantum yield of up to 52.80%. In addition, the research of photoluminescence properties under the guidance of terahertz spectroscopy technology leads to the preliminary discovery of a correlation between crystal packing and luminescence. It is found that the terahertz spectrum and absorption peak are strongly interdependent on C–H⋯π and π⋯π interactions, and the external weak interactions have negative effects on the luminescence performance. Herein, we predict that the terahertz spectroscopy analysis establishes a bridge between weak interactions (C–H⋯π and π⋯π interactions) and the photoluminescence properties, and puts forward a problem that should be noticed in designing Cu(I) complexes. [ABSTRACT FROM AUTHOR]

The diphosphine ligand N , N -bis(diphenylphosphanylmethyl)-aniline (bdppma) and PdCl2 afforded a Suzuki–Miyaura catalyst [(bdppma-)PdCl2 ] that was highly efficient at an ultralow catalyst loading (0.001 mol%) in 20:1 H2 O–EtOH. This low catalyst loading in an aqueous solvent system permitted simple product separation by direct filtration without the need for chromatography. The ligand bdppma imparted surprisingly better reactivity than that achieved with other bidentate diphosphine ligands, but the catalytic system had a slightly narrower substrate scope than some similar Pd catalysts reported previously. [ABSTRACT FROM AUTHOR]

The investigation of heterometallic Mo(W)–M′–S clusters (M′ = transition metals) has its genesis in the late 1970s with the identification of the nitrogenase iron–molybdenum cofactor (FeMoco) featuring a Mo–Fe–S double-cubane cluster core. This has led to the generation of a library of cluster skeletons subsequently used as building blocks for oligomers (OGs) and polymers, merging this field with the fascinating developments in supramolecular chemistry and coordination polymers (CPs). While resembling the general metal–ligand assembly to form CPs in one-pot, cluster-based OGs or CPs are conventionally prepared from Mo(W)–S synthons and Cu(i) salts in the presence of bridging ligands. This review summarizes the synthesis of Mo(W)–Cu–S cluster-supported OGs and CPs through a two-step strategy involving preformed clusters. This stepwise approach facilitates clean conversion, and is amenable to exquisite design protocols and yields products otherwise inaccessible via a direct one-pot method. We review the synthesis of OGs and CPs by cluster core upgrading, downgrading, ligand substitution, and cluster aggregation reactions, together with the optical and host–guest properties of the products. In doing so, we demonstrate the power and generality of this strategy for assembling these unique materials and offer clues on how to adapt this less practiced method to preparing extended molecular assemblies with potentially intriguing properties. [ABSTRACT FROM AUTHOR]

Reactions of a P–N hybrid ligand, N,N-bis(diphenylphosphanylmethyl)-3-aminopyridine (3-bdppmapy), with silver oxysalts including AgNO3, AgOAc, AgBz (Bz = benzoate) and AgSal (Sal = salicylate) under different reaction conditions give rise to seven coordination compounds {[Ag4(μ–η,η-NO3)2(μ–η,η2-NO3)2](3-bdppmapy)2}n (1), {[Ag4(μ–η,η2-NO3)4](3-bdppmapy)2}n (2), {[Ag2(μ–η2-OAc)(μ–η,η2-OAc)]2(3-bdppmapy)2}n (3), [Ag2(Bz)(μ–η,η2-Bz)(H2O)]2(3-bdppmapy)2 (4), {[Ag4(μ–η2-Bz)2(μ–η,η2-Bz)2](3-bdppmapy)2}n (5), {Ag(Sal)(3-bdppmapy)}n (6) and {[Ag4(Sal)2(μ–η,η2-Sal)2](3-bdppmapy)2}n (7). Single crystal X-ray analyses reveal that 1, 5 and 7 have similar 1D chain structures constructed by [Ag4(μ–η2-Ox)2(μ–η,η2-Ox)2] units (1: Ox− = NO3−; 5: Ox− = Bz−) or [Ag4(Sal)2(μ–η,η2-Sal)2] units (7) and double 3-bdppmapy bridges. Compound 2 has a 2D layer structure derived from [Ag4(μ–η,η2-NO3)4] units and single 3-bdppmapy bridges. 3 displays another 2D layer structure formed by [Ag2(μ–η2-OAc)(μ–η,η2-OAc)] units and double 3-bdppmapy bridges. 4 shows a discrete tetranuclear structure formed by two [Ag2(Bz)(η,η2,μ-Bz)(H2O)] units and a pair of 3-bdppmapy bridges, while 6 adopts a 1D chain composed by [AgSal] units and single 3-bdppmapy bridges. 6 and 7 as representative samples display high catalytic activity toward the photodegradation of rhodamine B (RhB) in water. Compound 7 shows a better photocatalytic performance than that of 6, which correlates well with the differences in their anodic photocurrent responses and their HOMO–LUMO energy gaps derived from the density function theory (DFT) calculations. The formation of 6 and 7 from AgSal and 3-bdppmapy provides a new approach to the design and assembly of Ag(i)-supported CPs with interesting structural architectures and higher photocatalytic activity. [ABSTRACT FROM AUTHOR]

The reaction of 3-aminopyridine with formaldehyde afforded a clamplike ligand, 3,7-di(3-pyridyl)-1,5-dioxa-3,7-diazacyclooctane (L). The diffusion of a CH2Cl2 solution of L into an MeCN solution of CuX produced one decanuclear cluster [Cu10Cl10(L)4] ( 1) and two tetranuclear clusters [Cu4X4(L)2(MeCN)2] [X = Br ( 2), I ( 3)]. Compound 1 possesses a unique [Cu10Cl10] cluster core consisting of two stairlike [Cu5Cl5] fragments that share two μ6-Cl and two μ-Cl atoms. Compounds 2 and 3 have a stairlike [Cu4X4] cluster core that is anchored by two L ligands. The trans configuration of the two pyridyl groups of the free L ligand was converted into the cis configuration of the two pyridyl groups of each bridging L ligand in 1- 3. The photoluminescence properties of 1- 3 in the solid state were also investigated. [ABSTRACT FROM AUTHOR]

Abstract: Reactions of PdCl2·2H2O with 2equiv. of 4-(trimethylammonio)benzenethiolate (Tab) (prepared in situ from a mixture of TabHPF6 and Et3N in MeOH) and seven phosphine ligands: PPh3, 1,1-bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda), and 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda), afforded a family of mononuclear and dinuclear Pd(II)/Tab/phosphine complexes, [Pd2(PPh3)2(Tab)2(μ-Tab)2](PF6)4 (1), [Pd2(dppm)2(Tab)2(μ-Tab)](PF6)4 (2), [Pd2(dppb)(Tab)2(μ-Tab)2]Cl4 (3), [PdL(Tab)2](PF6)2 (4: L=dppe; 5: L=dppp) and {[PdL(Tab)2]2}Cl4 (6: L=dppeda; 7: L=dpppda). These compounds were characterized by elemental analysis, IR spectra, UV–Vis spectra, 1H and 31P{1H} NMR, electrospray ionization (ESI) mass spectra and single-crystal X-ray diffraction. In the structure of 1–7, each Pd(II) adopt an approximate square planar coordination geometry. The results provide an interesting insight into the chemistry of palladium(II)/thiolate/phosphine complexes. [Copyright &y& Elsevier]

Abstract: Reaction of silver nitrate with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in the presence of aminothiocarbamide in CH2Cl2/MeOH afforded an unexpected and low-yield binuclear complex [Ag2(dppatc)2](NO3)2·2MeOH (dppatc=N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) (1). An X-ray analysis revealed that the [Ag2(dppatc)2]2+ dication of 1 contains a centrosymmetric double half-open cage structure in which two Ag centers are bridged by a pair of the heteroscopionate dppatc ligands via four Ag-μ-S and four AgThe in situ-formed dppatc ligand in 1 could be readily generated by one-pot and high-yield reaction of diphenylphosphine with formaldehyde and aminothiocarbamide. Further reaction of AgNO3 with dppatc could produce 1 in a relatively high yield. The results provided an efficient route to the synthesis of dppatc and also an interesting insight into its coordination chemistry. [Copyright &y& Elsevier]

Reactions of a gold(i) thiolate complex [Au(Tab)2]2(PF6)2(Tab = 4-(trimethylammonio)benzenethiolate) with equimolar 1,2-bis(diphenylphosphine)ethane (dppe), 1,3-bis-(diphenylphosphine)propane (dppp) or 1,4-bis-(diphenylphosphine)butane (dppb) in MeOH–DMF–CH2Cl2gave rise to three polymeric complexes [Au2(Tab)2(dppe)]2(PF6)4·2MeOH (1·2MeOH), [Au2(Tab)2(dppp)]Cl2·0.5MeOH·4H2O (2·0.5MeOH·4H2O), and [Au4(μ-Tab)2(Tab)2(dppb)](PF6)4·4DMF (3·4DMF), respectively. Analogous reaction of 1with dppb in DMF/C2H4Cl2produced one tetranuclear complex [Au2(μ-Tab)(Tab)2]2Cl4·2DMF·4H2O (4·2DMF·4H2O). Complexes 1–4were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H and 31P{1H} NMR and single crystal X-ray analysis. Compounds 1and 2consist of [Au(Tab)]2dimeric fragments that are bridged by dppe or dppp ligands to form a 1D linear chain extending along the aaxis. For 3, each [Au4(Tab)2(μ-Tab)2] fragment is linked by a pair of dppb ligands to afford another 1D chain extending along the caxis. For 4, the four [Au(Tab)]+fragments are linked by two Au–Au bonds and two doubly bridging Tab ligands to form a {[Au(Tab)]4(μ-Tab)2} chair-like cyclohexane structure. Hydrogen-bonding interactions in 2and 4lead to the formation of interesting 2D hydrogen-bonded networks. The luminescent properties of 1–4in solid state were also investigated. [ABSTRACT FROM AUTHOR]

Solvothermal reactions of CuI with four flexible N-heterocyclic ligands, 1,2-bis(4-pyridyl)ethane (bpe), 1,1′-(1,4-butanediyl)bis-1H-benzimidazole (bbbm), 1,1′-(1,4-butanediyl)bis-1H-benzotriazole (bbbt), and 1,1′-(1,5-pentanediyl)bis-1H-benzimidazole (pbbm), afforded four new [CunIn]-based coordination polymers, [Cu3I(μ-I)(μ3-I)(bpe)3]n(1), {[CuI(bbbm)1.5]·0.25MeCN}n(2), and [Cu4(μ3-I)4L2]n(3: L = bbbt; 4: L = pbbm), respectively. Compounds 1–4were characterized by elemental analysis, IR and X-ray crystallography. 1consists of an unique 2D network in which 1D [CuI(bpe)]nzigzag chains are embroidered alternatively onto the two faces of a 2D [Cu4(μ-I)2(μ3-I)2(bpe)2]nlayer through pairs of bpe bridges. 2contains a 66-membered metallomacrocyclic [CuI(bbbm)1.5]6unit that fuses with its neighbouring ones viasharing Cu atoms to form a 2D (6,3) layer network. 3or 4contains a cubanelike [Cu4(μ3-I)4] core, which works as a cross-shaped four-connecting node to link its four equivalent units to form a 2D (4,4) cross-shaped network (3) or acts as a Y-shaped three-connecting node to connect its three equivalent ones to form a 1D double chain (4). In addition, the photoluminescent properties of 1–4in solid state at ambient temperature were also investigated. [ABSTRACT FROM AUTHOR]

Abstract: Diffusion reactions of CuI with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine) (dppeda) and 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) in MeCN/toluene in a zigzag glass tube or solvothermal reactions of CuI and dppeda or dpppda in MeCN produced two [Cu x I x ]-based coordination polymers, [Cu2I2(dppeda)]·2MeCN (1·2MeCN) and [Cu4I4(dpppda)]·MeCN (2·MeCN), respectively. Both compounds were characterized by elemental analysis, IR spectroscopy, 1H and 31P{1H} NMR, ESI-MS and thermogravimetric analysis, and their structures were determined by single crystal X-ray diffraction. In 1, [Cu2I2] cores are interconnected by dppeda ligands in a μ-η 2:η 2 end-to-end mode to form a 1D chain, while in 2 stair-like [Cu4I4] cores are linked by dpppda ligands in a unique Z-shaped μ-η 2:η 2 side-by-side mode to produce the other kind of 1D chain. [Copyright &y& Elsevier]

Abstract: The solvothermal reactions of AgNO3, NaN3, with benzonitrile or 4-cyanopyridine in methanol/water yield two novel metal–organic coordination polymers, [Ag(μ3-phtta)] n (1) (phtta=5-phenyltetrazolate) and {Ag[μ4-(4-pytta)]} n (2) [4-pytta=5-(4-pyridyl)tetrazolate], respectively. The two reactions were involved in the in situ formation of 5-aryl-substituted tetrazolate ligands (phtta and pytta) through [2+3] cycloaddition reactions of azide anion with benzonitrile or 4-cyanopyridine. Compounds 1 and 2 were characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Compound 1 has a one-dimensional double-chain structure in which centrosymmetric dimeric [Ag(phtta)]2 units are interconnected by four Ag–N bonds. These double-chains are further stacked into a 2D layer network through π–π interactions between tetrazolyl rings and interactions between Ag+ and phenyl group or tetrazolyl ring. Compound 2 has an intriguing 3D non-interpenetrated supramolecular structure in which a 2D layer network with (4.82)Ag(4.82)pytta topology holds the adjacent layers together via interactions of Ag+ ions in one layer with 4-N atoms of pytta ligands in the other. Photoluminescence studies revealed that solids 1 and 2 exhibit strong blue fluorescent emissions at λ max =422 and 390nm (λ ex =345nm), respectively, at ambient temperature. [Copyright &y& Elsevier]

The orthorhombic (space group Pna21) title compound, [Ag(C7H6NO2)]n, is a polymorph of the known monoclinic (P21/n) variant of this stoichiometry [Smith, Lynch & Kennard (1999). Aust. J. C'hem. 52, 325-327]. In the title compound, the Ag atom shows linear coordination to one 0 and one N atom [Ag—O = 2.138 (5) Å, Ag—N = 2.153 (4) Å and O—Ag—N = 173.55 (18)°]. In the monoclinic form, the Ag coordination to two O atoms and one N atom can be described as Y-shaped or distorted trigonal planar. Weak Ag…Ag interactions, aromatic π-π stacking and N—H…O hydrogen-bond inter- actions help to establish the crystal packing in the title compound. [ABSTRACT FROM AUTHOR]

Abstract: In the absence of any additional ligands, the efficient N-arylation of nitrogen-containing heterocycles with aryl iodides catalyzed by relative low catalyst amount of Cu(OAc)2·H2O was developed. This simple catalytic system is involved in the C–N cross-coupling reaction and works for a variety of pyrazole, pyrrole, imidazole, triazole, indole, benzoimidazole, benzotriazole, carbazole, and anilines as well as aryl iodides with different electronic properties. Highly efficient copper(II)-catalyzed N-arylation protocol was established. [Copyright &y& Elsevier]

Abstract: Reactions of 25,26,27,28-tetrahydroxy-calix[4]arene (1) with 4 equiv. of m-carboxybenzenediazonium chloride in the presence of NaOAc∙3H2O in DMF produced a new azo calix[4]arene [H4L] (2) (H4L=5,11,17,23-tetrakis[(m-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]arene) in 96% yield. Hydrothermal reactions of Cd(NO3)2·4H2O with H4L at 90°C under pH=5.0–6.0 gave rise to a coordination polymer {[H3O]2[Cd7L4(DMF)4(EtOH)2(H2O)2]·5DMF·11.5EtOH·H2O}n (3). Compound 3 was characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Compound 3 consists of a 3D framework with an unprecedented (3346526371)(364135861) topology. The thermal properties of 2 and 3 were also investigated. [Copyright &y& Elsevier]

Abstract: Solvothermal reactions of CdSO4·8/3H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) and HCl in H2O, MeOH or EtOH afforded three coordination complexes [Cd5Cl2(μ-Cl)4(μ3-Cl)2(η,η,η-μ3-SO4)2(H2O)2(Htitmb)2] n (1), [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2(MeOH)2(titmb)2] n (2) and [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2] (3), respectively. All the compounds were characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 has a 1D chain in which each centrosymmetric double butterfly-shaped [Cd5Cl2(μ-Cl)4(μ3-Cl)2(H2O)2] unit interlinks with its equivalent ones via two couples of η,η,η-μ3-SO4 anions and two pairs of the Htitmb ligands. Compound 2 consists of one centrosymmetric [Cd5Cl2(μ-Cl)2(η,η,η-μ3-SO4)2(MeOH)4(titmb)2] unit that interconnects with equivalent ones via sharing Cd3 and its symmetry-related ones, forming a 1D zigzag chain. Compound 3 consists of a [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2] unit linked by a pair of titmb ligands. The results may provide some insight into solvent effects on the formation of different coordination compounds from the same components. [Copyright &y& Elsevier]

Abstract: Treatment of a preformed cluster {(η5-C5Me5)WS3}3Cu7(MeCN)9](PF6)4 (1) in MeCN with excess pyridine afforded a tetranuclear cationic cluster [(η5-C5Me5)WS3Cu3(Py)6](PF6)2 (2). On the other hand, reactions of 1 with excess PPh3 under the presence of LiBr gave rise to the other tetranuclear cationic cubane-type cluster [(η5-C5Me5)WS3Cu3Br(PPh3)3](PF6) (3) while analogous reactions of 1 with dppm and LiCl followed by addition of excess pyridine generated an intriguing pentanuclear cationic cluster [(η5-C5Me5)WS3Cu4(Py)Cl(dppm)2](PF6)2 (4). Compounds 2–4 were fully characterized by spectroscopy and X-ray crystallography. The cluster dication of 2 adopts an incomplete WS3Cu3 cubane-like structure while the cluster cation of 3 contains a WS3Cu3Br cubane-like structure. The structure of the cluster dication of 4 consists of an unique WS3Cu4Cl framework in which an open cubane-like WS3Cu3Cl fragment and a Cu(dppm)2 fragment are connected by one Cu–Cl bond and two Cu–dppm–Cu bridges. The optical limiting (OL) properties of the MeCN solutions of 1–4 were investigated with 7-ns laser pulses at 532nm. [Copyright &y& Elsevier]

The article presents chemical equations related to the article "Versatile Palladium(II)-Catalyzed Suzuki-Miyaura Coupling in Ethanol with a Novel, Stabilizing Ligand" by J.-J. Ning and others, published in the periodical "Tetrahedron" in 2015.

Abstract: Reactions of Zn(NO3)2∙6H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) in the presence of 1,4-benzenedicarboxylic acid (1,4-H2BDC) or 1,3-benzenedicarboxylic acid (1,3-H2BDC) under hydrothermal conditions afforded one 1D and one 2D coordination polymers [Zn3(titmb)2(1,4-BDC)3(H2O)6] (1) and [Zn2(titmb)(1,3-BDC)2(H2O)] (2), respectively. Similar reactions of Zn(NO3)2∙6H2O with 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bitmb) and 1,4-H2BDC gave rise to one 2D coordination polymer [Zn2(bitmb)2(1,4-BDC)2] (3). Compound 1 has a 1D linear chain formed from linking 24-membered [Zn2(titmb)2] metallamacrocycles and [Zn(1,4-BDC)(H2O)2] units via imidazolyl groups of titmb ligands. Compound 2 has a 2D network assembled from connecting spiral [Zn n (1,3-BDC) n ] chains with titmb linkers, while compound 3 also has a 2D network formed by linking 24-membered [Zn2(bitmb)2] metallamacrocycles via 1,3-BDC bridges. The ligands titmb and bitmb in compounds 1–3 adopt less-common cis–trans–trans and cis–trans conformations, respectively. Their thermal and photoluminescent properties were also investigated. [Copyright &y& Elsevier]

Abstract: Two new self-assemblies based on two zinc porphyrins substituted at the meso-positions with different donor units (denoted as ZnP1 and ZnP2) and isonicotinic acid (A) by metal–ligand axial coordination have been designed and immobilized on the double-layer nanostructured TiO2 film-coated highly transparent FTO conducting glass electrode in a photosynthesis device. These cells were also measured under irradiance of 100mWcm−2 AM 1.5G sunlight. The results reveal that the performance of ZnP2-A outperforms that of ZnP1-A. The UV–vis absorption spectra, fluorescence spectra, molecular orbital (MO) patterns, and HOMO–LUMO energy gaps of these assemblies were also investigated to further demonstrate the photovoltaic behavior of these cells. [Copyright &y& Elsevier]

Hydrothermal reactions of NiCl2·6H2O or CdCl2·2.5H2O with 4,4′-bis(1-imidazolyl)bibenzene (bimb) and 5-oxyacetate isophthalic acid (H3OAIP) resulted in the formation of two coordination polymers [Ni2(HOAIP)2(bimb)3(H2O)2] n (1) and [Cd3(OAIP)2(bimb)(H2O)2] n ·2nH2O (2), respectively. Compounds 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. 1 exhibits three-fold interpenetrating 3D architecture with a (44 ·65 ·8) Schläfli symbol in which 1D [Ni(HOAIP)] n chains are interlinked by bimb ligands. In 2, the two [Cd2(OAIP)4] and [Cd2(OAIP)4(H2O)4] units are interconnected by OAIP and bimb to afford a 3D network with a unique (4·82)4(42 ·68 ·85)2(86) Schläfli symbol. The results showed that metal ions did exert great influence upon the coordination modes and the geometrical conformations of ligands and the topological structures of the final products. Their thermal and photoluminescent properties were also investigated. [ABSTRACT FROM AUTHOR]

Reactions of N,N-bis(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) with [Ag(MeCN)4]ClO4 or AgX (X = Cl, Br, I, SCN, CN) afforded a family of oligomeric and polymeric complexes: [Ag2(MeOH)(bdppmapy)2](ClO4)2 (1), [AgCl(bdppmapy)] (2), [AgBr(bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN(bdppmapy)] (5), [{(η2-bdppmapy)Ag(μ-CN)AgCN}2(μ-bdppmapy)] (6), [Ag4(μ-CN)4(μ-bdppmapy)] (7), and [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-CN)6] (8). Compounds 1–8 were characterized by elemental analyses, IR spectra, 1H and 31P{1H} NMR, electrospray ionization (ESI) mass spectra, powder X-ray diffraction (XRD), and single-crystal X-ray diffraction. Compounds 1–3 and 5 hold a one-dimensional (1D) chain in which [Ag(MeOH)]+ or [AgX] motifs are linked by bdppmapy bridges. Compound 6 has a tetrameric framework in which two linear [(η2-bdppmapy)Ag(μ-CN)AgCN] fragments are connected by a μ-bdppmapy ligand. Compound 7 contains a 1D staircase chain in which two zigzag [Ag(μ-CN)]n chains are linked by pairs of μ-bdppmapy bridges. Compound 8 possesses an unprecedented three-dimensional (3D) structure in which the channels of one 3D anionic [Ag10(μ-CN)12]n2n– net are plugged with 1D cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chains. The degradation versus expansion of the bulk AgX frameworks do affect the formation of [AgaXb]-based oligomers and polymers when AgX is treated with bdppmapy. The photoluminescent properties of 1–8 in the solid state were also investigated. Treatment of [Ag(MeCN)4]ClO4 or AgX (X = Cl, Br, I, SCN, CN) with N,N-bis(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) gave rise to a set of oligomeric and polymeric complexes: [Ag2(MeOH)(bdppmapy)2](ClO4)2 (1), [AgCl(bdppmapy)] (2), [AgBr (bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN(bdppmapy)] (5), [{(η2-bdppmapy)Ag(μ-CN)AgCN}2(μ-bdppmapy)] (6), [Ag4(μ-CN)4(μ-bdppmapy)] (7), and [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-CN)6] (8). Compounds 1−8 were characterized by elemental analyses, IR spectra, 1H and 31P{1H} NMR, electrospray ionization (ESI) mass spectra, powder X-ray diffraction (XRD), and single-crystal X-ray diffraction. The photoluminescent properties of 1−8 in the solid state were also investigated. [ABSTRACT FROM AUTHOR]

Abstract: The solvothermal reactions of Zn(NO3)2∙6H2O with 1,4-benzenedicarboxylic acid (1,4-H2bdc) and 1,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)butane (dmpzb) or 1,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)hexane (dmpzh) afforded two three-dimensional coordination polymers [Zn3(1,4-bdc)3(dmpzb)] n (1) and [Zn2(1,4-bdc)2(dmpzh)] n (2), respectively. Compounds 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single crystal X-ray diffraction. Compound 1 has an 8-connected 3D net (a 364185262 Schläfli symbol) assembled from trinuclear [Zn3(1,4-bdc)3] units and 1,4-bdc and dmpzb bridges. Compound 2 has a 6-connected 3D net (with a 485463 Schläfli symbol) constructed from binuclear [Zn2(1,4-bdc)2] units and 1,4-bdc and dmpzh linkers. The solid state luminescent and thermal stability properties of 1 and 2 at ambient temperature were also investigated. The results showed that the spacer lengths of bipyrazol-based ligands did affect the topological structures of zinc(II) coordination polymers. [Copyright &y& Elsevier]

Abstract: The chemistry of metal complexes of the zwitterionic ammonium thiolates has expanded dramatically in the recent years. This review is intended to summarize the synthesis and crystal structures of groups 11 and 12 metal zwitterionic ammonium thiolate complexes. Seven methods for the synthesis of these metal complexes of the zwitterionic ammonium thiolates are outlined: proton transfer reaction, precursor reaction, ligand exchange reaction, oxidation–reduction reaction, solid-state reaction, electrochemical reaction and hydro(solvo)thermal reaction. These metal complexes of the zwitterionic ammonium thiolates are classified according to the number of metal atoms; their specific structures are briefly discussed. [Copyright &y& Elsevier]