Four distinctive 1-D lanthanide carboxylate coordination polymers: Synthesis,crystal structures and spectral properties

Four novel lanthanide coordination polymers [Pr(mal)(OH)(bipy) · 2H₂O]_n (1), {[Dy¹(SBA)₃(H₂O)₂][Dy²(SBA)₃(H₂O)₂] · 4H₂O}_n (2), {[Tb(OHnic)(Onic)(H₂O)₅ · (OHnicH)] · H₂O}_n (3) and {[Sm(OHnic)(Onic)(H₂O)₅ · (OHnicH)] · H₂O}_n (4) (Hmal = maleic acid, HSBA = 4-sulfobenzoic acid, OHnicH = 6-hydroxynicotinic acid and bipy = 2,2′-bipyridine) have been synthesized and determined by single crystal X-ray diffraction. Complex 1 is a 1-D helical chain with seven-coordinated praseodymium centers. Complex 2 forms 1-D chain-like molecular structure containing two crystallographically unique dysprosium centers, the Dy¹ center is seven-coordinated while Dy² is eight-coordinated. The isomorphous complexes 3 and 4 exhibit an unprecedented 1-D chain-like polymeric structure through hydroxyl oxygen atoms of bridging Onic²⁻ anions linking up the neighboring central ions, and there exist three types of 6-OHnicH ligands in the structural unit which is rare for lanthanide carboxylate complexes. The photophysical properties of these complexes were studied using ultraviolet absorption spectra, fluorescence excitation and emission spectra.     

1D coordination polymers of silver(I) and copper(II) based on bis(N-heterocyclic carbene) ligands: Synthesis and structural studies

The alkyl chain-linked diimidazolium (or dibenzimidazolium) salts, 1,1′-diethyl-4,4′-tetramethylene-diimidazolium-diiodide (L¹H₂·I₂) and 1,1′-diethyl-3,3′-trimethylene-dibenzimidazolium-diiodide (L²H₂·I₂), and their silver(I) and copper(II) coordination polymers, [L¹AgI]_n (1) and [L²Cu₂I₄]_n (2), have been prepared and characterized. Complex 1 is a 1D helical polymer generated by bidentated carbene ligands (L¹) and Ag(I) atoms. The 1D polymer of 2 is formed by bidentated carbene ligands (L²) and coplanar quadrilateral Cu₂I₂ units. 3D supramolecular frameworks in the crystal packings of 1 and 2 are formed via intermolecular weak interactions, including C–H···π contacts, π–π interactions and C–H···I hydrogen bonds.     

Novel hydridotris(pyrazolyl)borate ruthenium(II) complexes containing the water-soluble phosphane 1,3,5-triaza-7-phosphaadamantane: Synthesis and evaluation of DNA binding properties

A series of half-sandwich ruthenium(II) complexes containing κ³(N,N,N)-hydridotris(pyrazolyl)borate (κ³(N,N,N)-Tp) and the water-soluble phosphane 1,3,5-triaza-7-phosphaadamantane (PTA) [RuX{κ³(N,N,N)-Tp}(PPh₃)_2−n(PTA)_n] (n = 2, X = Cl (1), n = 1, X = Cl (2), I (3), NCS (4), H (5)) and [Ru{κ³(N,N,N)-Tp}(PPh₃)(PTA)L][PF₆] (L = NCMe (6), PTA (7)) have been synthesized. Complexes containing 1-methyl-3,5-diaza-1-azonia-7-phosphaadamantane(m-PTA) triflate [RuCl{κ³(N,N,N)-Tp}(m-PTA)₂][CF₃SO₃]₂ (8) and [RuX{κ³(N,N,N)-Tp}(PPh₃)(m-PTA)][CF₃SO₃] (X = Cl (9), H (10)) have been obtained by treatment, respectively, of complexes 1, 2 and 5 with methyl triflate. Single crystal X-ray diffraction analysis for complexes 1, 2 and 4 have been carried out. DNA binding properties by using a mobility shift assay and antimicrobial activity of selected complexes have been evaluated.     

Photocatalytic properties of new cyclopentadienyl and indenyl rhodium(I) carbonyl complexes with water-soluble 1,3,5-triaza-7-phosphaadamantane (PTA) and tris(2-cyanoethyl)phosphine

Reactions of [(η⁵-R)Rh(CO)₂] (R = cp, ind) with water-soluble phosphines (L = 1,3,5-triaza-7-phosphaadamantane and tris(2-cyanoethyl)phosphine) give the new rhodium(I) complexes of the types [Rh(η⁵-cp)(CO)(PTA)] (1), [Rh(η⁵-cp)(CO)(P(CH₂CH₂CN)₃)] (2), [Rh(η⁵-ind)(CO)(PTA)] (3) and [Rh(η⁵-ind)(CO)(P(CH₂CH₂CN)₃)] (4) in isolated yields of 52-75%. All these compounds have been fully characterized by IR, ¹H, ³¹P{¹H} and ¹³C{¹H} NMR, FAB-MS spectroscopies and elemental analyses. Reactivity for the substitution of phosphine is greater for [(η⁵-ind)Rh(CO)(L)] comparing to [(η⁵-cp)Rh(CO)(L)] because of a flexibility of the indenyl ligand to undergo facile η⁵-η³ coordinative isomerizations. The obtained complexes are active catalyst precursors for the dehydrogenation of propan-2-ol, octane and cyclooctane under photoassisted conditions without any organic hydrogen transfer acceptors, giving TOFs of 26-56 using 3 as precatalyst.     

Synthesis of a new N,N-ethane-1,2-bis(4-methoxyphenyl)carbothioamide ligand and its Cu(I) and Ag(I) complexes

[Cu(H₂L)(PPh₃)₂]NO₃ · 0.5H₂O (2) and [Ag(H₂L)(PPh₃)₂]NO₃ · 0.5H₂O (3) complexes of a new flexible thioamide ligand; N,N′-ethane-1,2-bis(4-methoxyphenyl)carbothioamide H₂L (1) have been synthesized using PPh₃ as a coligand. The synthesized compounds have been characterized with the help of elemental analyses, IR, ¹H, ¹³C and ³¹P NMR spectroscopy. The ligand and its Cu(I) complex have been studied by single crystal X-ray crystallography. The ligand acts as a neutral S-donor and forms a nine-membered chelate ring in [Cu(H₂L)(PPh₃)₂]NO₃ · 0.5H₂O. The molecular packing is stabilized by an anionic cavity formed by intermolecular hydrogen bonding between the basal plane of the complex molecule and the nitrate ions. The square shaped columnar channel has dimensions of 5.489(25) [N(11)–H(11A)?O(13)?H(21A)N(21)] × 3.693(7) [N(11)–C(11)–C(21)–N(21)] Å.     

Anion-driven Ag(I) coordination architectures: structural diversity and photoluminescence behaviors

To observe anion impact on structural diversity of coordination architectures, three 1-D Ag(I) complexes with distinct features have been prepared, {[Ag(bpbib)₂(NO₃)]·C₃NH₉O)}_n (1), [Ag₂(bpbib)₂·(BF₄)₂]_n (2), and [Ag₂(bpbib)₂·(ClO₄)₂]_n (3), by the reactions of 4,4′-bis((2-(pyridin-2-yl)-¹H-benzo[d]imidazol-1-yl)methyl)biphenyl (bpbib) with Ag(I) salts. Complex 1 is a 1-D helical chain, whereas 2 and 3 bear ligand-unsupported Ag(I)···Ag(I) interaction-directed 1-D structural motif, with synergetic working of flexible organic linker and anions. All complexes exhibit strong triplet state emission at cryogenic temperatures, which profits from the reduction of nonradiative transitions.     

Synthesis,crystal structure and properties of a silver(I) complex with 2-(1H-1,2,4-triazol-1-yl) acetic acid

The treatment of 2-(1H-1,2,4-triazol-1-yl) acetic acid (Htza) with AgClO₄ resulted in [Ag₃(tza)₂(ClO₄)] _n . Its crystal structure was characterized by X-ray crystallography. Each pair of adjacent Ag1 atoms, separated at 2.954 Å, is bridged by the bidentate carboxylate. Each Ag2 is coordinated in an exactly linear geometry by two triazole nitrogens from two tza^? ligands. Solid state fluorescent measurements have a ligand-based emission at 415 nm. Thermal properties were also investigated.     

Synthesis and Crystal Structure of Binuclear Silver(I) Complex with 2-nitro-(2-pyridylsulfanylmethyl)benzene

1 INTRODUCTION Metallosupramolecular species with metal-metal interactions have been designed and synthesized due to their potential applications as functional materi- als[1]. For Ag(I) coordination compounds, short Ag(I) –Ag(I) separations have been found in many bi- and polynuclear complexes[2~4], and these short metal- metal distances have been attributed to the ligand ar- chitecture[5, 6]. Thus, the rational design of bi- and polynuclear Ag(I) complexes must recognize the in- here…     

三个二羧酸配体配位聚合物的合成、结构表征和荧光性质

以羧酸配体 2,2''-(1,4-亚苯基双(亚苯基))双(硫二基)二苯甲酸(H₂L¹)和 2,2''-(2,3,5,6-四甲基-1,4-亚苯基)双(亚甲基）双(硫二基)二苯甲酸(H₂L²)分别与金属盐反应,通过溶剂热方法合成了 3个配位聚合物：{[Ni(L¹)(H₂O)₄]·2H₂O}_n (1)、[Zn(L¹)(DMA)₂]_n(2)和[Co(L²)(DMF)₂]_n (3),其中DMA=N,N-二甲基乙酰胺,DMF=N,N-二甲基甲酰胺。对配合物1~3进行了单晶X射线衍射、元素分析、红外光谱、热重分析、粉末X射线衍射和固体紫外可见光谱测试和表征。单晶X射线衍射表明：3个配合物均为一维锯齿形链状结构,并通过氢键作用形成三维骨架,且配体均表现为反式构象。此外,对配合物2固态荧光性质进行了研究。     

Synthesis of the water-soluble [Rh(Tpms)(CO)(PTA)] compound, the first transition metal complex bearing the 1,3,5-triaza-7-phosphaadamantane (PTA) and the tris(1-pyrazolyl)methanesulfonate (Tpms) ligands

The water-soluble Rh^I compound [Rh(Tpms)(CO)(PTA)] (1) (Tpms = O₃SC(pz)₃⁻, PTA = 1,3,5-triaza-7-phosphaadamantane) has been easily prepared in high yield by a single-pot reaction of [{Rh(CO)₂(μ-Cl)}₂] with PTA and the tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms), in a CH₂Cl₂/MeOH solution at room temperature. This synthetic strategy can be easily applied to the preparation of general [Rh(Tpms)(CO)(L)] (L = phosphine) complexes and constitutes a substantial improvement over the previously described procedures. Compound 1 is air stable in the solid state and water-soluble, affording stable solutions under an inert atmosphere. It has been characterized by IR, ¹H, ³¹P{¹H} and ¹³C{¹H} NMR spectroscopies, elemental and single crystal X-ray diffraction structural analyses. The solid state structure of 1 has a square-planar geometry with the Tpms ligand coordinating the metal centre in a (κ²: N,N) bipodal mode. The title compound has also been investigated by cyclic voltammetry in CH₃CN, and values of the E_L Lever and P_L Pickett electrochemical parameters (which measure the ligand net electron-donor character) are proposed for the PTA ligand. Complex 1 represents the first example of a transition metal complex bearing both PTA and Tpms (or any other tris(1-pyrazolyl)methane or derivative) ligands.     

三个二羧酸配体配位聚合物的合成、结构表征和荧光性质

以羧酸配体2,2''-（1,4-亚苯基双（亚甲基））双（硫二基）二苯甲酸（H₂L¹）和2,2''-（2,3,5,6-四甲基-1,4-亚苯基）双（亚甲基）双（硫二基）二苯甲酸（H₂L²）分别与金属盐反应,通过溶剂热方法合成了3个配位聚合物：{[Ni（L¹）（H₂O）₄]·2H₂O}_n （1）、[Zn（L¹）（DMA）₂]_n （2）和[Co（L²）（DMF）₂]_n （3）,其中DMA=N,N-二甲基乙酰胺,DMF=N,N-二甲基甲酰胺。对配合物1~3进行了单晶X射线衍射、元素分析、红外光谱、热重分析、粉末X射线衍射和固体紫外可见光谱测试和表征。单晶X射线衍射表明：3个配合物均为一维锯齿形链状结构,并通过氢键作用形成三维骨架,且配体均表现为反式构象。此外,对配合物2固态荧光性质进行了研究。     

Synthesis and coordination chemistry of a novel bidentate phosphine: 6-(diphenylphosphino)-1,3,5-triaza-7-phosphaadamantane (PTA-PPh2)

The upper rim of 1,3,5-triaza-7-phosphaadamantane (PTA) has been modified for the first time. Lithiation of PTA, with n-butyllithium, resulted in deprotonation of an alpha-phosphorus methylene and the formation of 1,3,5-triaza-7-phosphaadamantane-6-yllithium (PTA-Li). The chiral chelating phosphine 6-(diphenylphosphino)-1,3,5-triaza-7-phosphaadamantane (PTA-PPh2) was synthesized, in racemic form, by the reaction of PTA-Li with ClPPh2. PTA-PPh2 has been fully characterized in solution by multinuclear NMR spectroscopy and mass spectrometry and in the solid state by X-ray crystallography. The 31P NMR spectrum contains a pair of doublets at -19.8 and -100.1 ppm (d, (2)J(PP) = 65 Hz). Unlike PTA, the new bidentate phosphine, PTA-PPh2, is insoluble in aqueous solutions. Two group 6 metal carbonyl complexes, [M(CO)4(PTA-PPh2)] (M = W and Mo), were synthesized by the addition of PTA-PPh2 to cis-[M(CO)4(pip)2] and characterized by NMR spectroscopy, IR spectroscopy, and X-ray crystallography. Also reported are the solid-state structures of cis-[W(CO)4PTA2], cis-[W(CO)4(PTA)(PPh3)], and [W(CO)4DPPM] (DPPM = diphenylphosphinomethane). PTA-PPh2 appears to be sterically similar to and slightly more electron-donating than DPPM.     

Synthesis and structural characterization of a coordination polymer of silver(I) with saccharinate and nicotinamide

A silver(I)-saccharinato (sac) complex with nicotinamide (nia), [Ag(sac)(nia)] _n has been synthesized and characterized by elemental analysis, IR spectroscopy, DTA-TG analyses and single crystal X-ray diffractometry. The complex crystallizes in monoclinic space group P2₁/n with unit cell parameters of a=7.0258(4) Å, b=24.3784(10) Å, c=8.4301(5) Å, β=109.407(5)°, V=1361.85(13) ų and Z=4. [Ag(sac)(nia)] _n contains [Ag(sac)(nia)] units, which are doubly bridged by both nia and sac ligands, leading to a linear one-dimensional polymeric chains running along the a axis. The silver(I) ion has a highly distorted AgN₂O₂ tetrahedral geometry and the coordination polymer exhibits relatively short intra-chain ligand supported Ag···Ag separations of 3.1593(4) Å. The one-dimensional chains are crosslinked by N–H···O hydrogen bonds and aromatic π(sac)···π(nia) stacking interactions to generate a two-dimensional layer structure. IR spectra and thermal analysis data are in agreement with the crystal structure.     

Coordination polymers and discrete complexes of Ag(I)-N-(pyridylmethylene)anilines: synthesis,crystal structures and photophysical properties

Reactions of AgO₂C₂F₃ with (E)-N-(pyridylmethylene)aniline in which the pyridyl N is in the p- or m-position yielded two 1-D coordination polymers, [(AgO₂C₂F₃)₂(L_a)₂]_n (L_a = (E)-2,6-diisopropyl-N-(pyrid-3-ylmethylene)aniline) (1) and [(AgOC₂F₃)₂(L_d)₂]_n (L_d = (E)-2,6-diisopropyl-N-(pyrid-4-ylmethylene)aniline) (5), and three discrete complexes, [(AgO₂C₂F₃)₂(L_a)₄] (2), [AgO₂C₂F₃(L_b)₂] (L_b = (E)-N-(pyrid-4-ylmethylene)aniline) (3) and [(AgOC₂F₃)₂(L_c)₄] (L_c = (E)-2,6-dimethyl-N-(pyrid-4-ylmethylene)aniline) (4). The structures were determined by MS, FT-IR and NMR spectroscopies, elemental analysis and single crystal XRD. 1 is an organometallic coordination polymer with silver in η¹-arene coordination, but is a discrete dimeric complex 2 when crystallized from warm diethylether. The geometries around silver(I) in 1 and 4 are tetrahedral, ‘inverted seesaw’ in 2 and T-shaped in 3 and in all the anion seems to play a role. Ag(I) centers in 5 have distorted trigonal bipyramid and inverted seesaw geometries. The trifluoroacetate anions in these complexes display variable monodentate and short bridging coordination patterns. All complexes absorb and strongly emit UV-Vis radiation at room temperature.     

The effect of short alkane bridges in stability of bisbenzimidazole-2-ylidene silver(I) complexes: synthesis,crystal structure and antibacterial activity

Three bisbenzimidazolium salts, 3,3-(alkane-1,n-diyl)bisbenzylbenzimidazolium dibromide/dihexafluorophosphate (1a/b–3a/b) (where alkane?=?ethane, propane or butane and n?=?2, 3, or 4), were synthesized. The bromide salts were subsequently used as precursors to prepare their respective Ag(I)-NHC complexes via in situ deprotonation method. The successful formation of all bisbenzimidazolium salts and complexes were proved by elemental analysis, ¹H-NMR, ¹³C-NMR and FT-IR analyses. From single-crystal X-ray diffraction analyses, 4 has been established as a binuclear complex with the molecule arranged as in trans-conformation. Salts 1b–3b and Ag(I)-NHC complexes 4–6 were then screened for their antibacterial potential against E. coli (ATCC 25922) and S. aureus (ATCC 12600). All the bisbenzimidazolium salts do not show any activity against both bacteria while 4 exhibits the highest activity against both bacteria in all methods followed by 5 and 6.     

Ag(I) coordination polymer with pyrazine sulfonic acid: synthesis,crystal structure,and fluorescence property

A one-dimensional rigid, linear Ag(I) coordination polymer with pyrazine sulfonic acid, [Ag₂L₂?·?H₂O] _n (L?=?pyrazine sulfonic acid) has been synthesized and characterized by elemental analyses, infrared spectroscopy, thermogravimetric analysis, and X-ray crystallography. The structure determination shows Ag(I) centers linked by bridging pyrazine ligands to give a double-chain structure sustained by weak Ag-O and Ag-N interactions. The sulfonate and pyrazine are all involved in hydrogen bonding interaction. The interactions combine with weak π-π stacking to play deciding roles defining the supramolecular structures. A powder X-ray diffraction study implies good phase purity. Solid-state fluorescence quenching and thermal stability are also discussed.     

1D Chain and 3D framework of silver(I) organo-metallic polymers self-assembled with triptycene

For the purpose of investigating the coordination behavior of sterically congested alkenes and exploring the possibility of non-planar complexation in the polycyclic aromatic system for formation of extended polymeric networks, triptycene (tpty) has been studied with regard to its complexation with the silver(I) ion. The crystal structures of [Ag(tpty)(THF)₂](ClO₄) (1) and [Ag₆(tpty)₄(CF₃SO₃)₂(H₂O)₆](CF₃SO₃)₄ (2) have been determined by single-crystal X-ray diffraction. The polycyclic aromatic hydrocarbon triptycene is found to offer a potential site for complexation, which can be utilized to generate an interesting array of organo-metallic polymers with one-dimensional (1D) chain and three-dimensional (3D) porous frameworks.     

Two novel Ag(I) coordination polymers with triazoles derivatives: synthesis,crystal structures and biological activity

Two novel coordination polymers, [Ag(L₁)(NO₃)]_n 1 and [Ag(L₂)₂(ClO₄)]_n 2 [L₁ = 1‐(1‐benzotriazole‐yl‐)triazole, L₂ = 1‐(4‐chloro‐pyridazine‐yl‐)triazole] have been synthesized and characterized. Single‐crystal X‐ray analyses show that the Ag(I) atom is in a four‐coordinated distorted tetrahedron environment, which are linked by the coordinated nitrate group and L₁ into a two‐dimensional network in complex 1 . While in the complex 2 , the Ag(I) is also in a distorted tetrahedron environment consisting of four N atoms to present a one‐dimensional infinite chain, the intermolecular π? π stacking action extends further the repeated units into three‐dimensional topological framework. The biological activities of the title compounds have been studied. The results indicate that two ligands exhibit excellent radical‐scavenging activities and certain fungicidal activities, and both Ag(I) complexes only have good antibacterial activities. Furthermore, the studies on luminescent properties of the complexes in the solid state indicate that the Ag(I) complexes exhibit weaker fluoresce intensity than that of ligands at room temperature. Copyright © 2008 John Wiley & Sons, Ltd.     

Ionothermal syntheses and characterization of 2-D coordination polymers with 4-(1H-imidazol-1-yl) benzoic acid

4-(1H-imidazol-1-yl) benzoic acid and its coordination polymers [M(IBA)Cl] _n (M?=?Zn (1) and Co (2)) have been synthesized. Compounds 1 and 2 were obtained under ionothermal conditions and possess a 2-D laminar [M(IBA)] _n layer based on M₂(CO₂)₂ building blocks with coordinated chloride completing tetrahedral coordination of the metal. Compound 1 exhibits two photoluminescence emission peaks at 410 and 510?nm. The low-energy emission can be attributed to ligand-centered transition and the high-energy band can be assigned to ligand-to-metal charge transfer between the aromatic systems of the organic ligands and the 4s orbitals of Zn(II). The role of the ionic liquid in ionothermal synthesis and crystallization of 1 and 2 are briefly discussed.     

Copper(I) and silver(I) complexes of bridging bis(quinaldinyl)phenylphosphine oxide ligand

Abstract

A novel tertiary phosphine oxide containing two quinaldinyl substituents has been synthesized according to adapted literature procedures. Its coordination properties toward Cu(I) and Ag(I) were investigated and the resulting complexes were analyzed by single crystal X-ray diffraction. Multinuclear complexes are formed, wherein the ligand is bridging across two metal centers. Though for the silver complex, no argentophilic interactions are present. The copper complex was characterized further by multinuclear NMR spectroscopy at variable temperatures.