Structurally Diverse Divalent Metal Adamantanedicarboxylate Coordination Polymers with Hydrogen‐bonding Capable Dipyridyl Pillaring Ligands

Five new divalent metal coordination polymers containing either 1,3‐adamantanedicarboxylate (adc) or 1,3‐adamantanediacetate (ada) and pillaring dipyridyl ligands were prepared and structurally characterized by single‐crystal X‐ray diffraction. Using the V‐shaped linker 4,4′‐dipyridylamine (dpa), three new phases were isolated. {[Zn₂(ada)₂(dpa)₂] · 4.5H₂O}_n ( 1 ) shows a (4,4) grid topology with embedded octameric water clusters. {[Co(ada)(dpa)(H₂O)] · H₂O}_n ( 2 ) also manifests a 2D dimensionality, but with an intriguing novel (4)(12)(4.12⁵) looped topology. {[Cd(adc)(H₂O)₂] · H₂O}_n ( 3 ) did not incorporate dpa ligands during self‐assembly, but exhibits an uncommon 3‐connected 8³ etb network topology. [Co(ada)(ebin)]_n ( 4 ) [ebin = ethanediaminebis(nicotinamide)] possesses a (3,6) triangular net based on {Co₂(OCO)₂} dimeric units. {[Cd(adc)(ebin)] · 2H₂O}_n ( 5 ) also shows dimeric units, although linked into a decorated (4,4) grid topology. Magnetic susceptibility studies of compound 4 revealed a decrease in χ_mT product upon cooling, ascribed to antiferromagnetic coupling concomitant with single‐ion effects [g = 2.39(2) with D = 40(3) cm^–1 and J = –3.55(4) cm^–1]. Compounds 1 and 5 undergo blue‐violet fluorescence upon ultraviolet irradiation; the zinc derivative 1 shows potential as a sensor for the solution‐phase detection of nitrobenzene and m‐nitrophenol. Thermal decomposition behavior of the five new phases is also discussed.     

Crystal Structures,Magnetism, and Dye Degradation Catalytic Properties of Copper 2‐Methoxycarboxybenzoate Coordination Complexes

Copper coordination complexes containing the 2‐methoxycarboxybenzoate (2‐mcob) ligand show different topologies depending on the nature of the dipyridyl coligand. [Cu₂(2‐mcob)₂(ebin)]_n ( 1 ) [ebin = ethanebis(isonicotinamide)] shows a ladder structure based on anti‐syn bridged [Cu(OCO)]_n chain motifs. [Cu₂(2‐mcob)₂(bbin)(H₂O)₂] ( 2 ) [bbin = butanebis(isonicotinamide)] displays a dimeric molecular structure. [Cu₂(2‐mcob)₂(hbin)]_n ( 3 ) [hbin = hexanebis(isonicotinamide)] manifests a ladder structure very similar to that of 1 . {[Cu(2‐mcob)(dpa)] · H₂O}_n ( 4 ) [dpa = bis(4‐pyridyl)amine] shows a chain coordination polymer structure. All four materials showed significant promise as heterogeneous degradation catalysts for Congo Red dye in aqueous suspension under ultraviolet irradiation. Variable temperature magnetic susceptibility experiments for 1 indicated the presence of weak antiferromagnetic exchange (g = 2.059(2), J = –0.84(2) cm^–1). Thermal degradation behavior is also discussed.     

Novel 3-D Supramolecular Architectures Constructed from Zn^2＋ ions, Oxybis（4-benzoate） and Di（2-pyridyl）amine Ligands

Using the V-shaped oba dianions as bridging ligands and dpa molecules as terminal ligands, a new 1D helical coordination-polymeric chain, [Zn（oba）（dpa）]n [oba=oxybis（4-benzoate）, dpa=di（2-pyridyl）amine], was synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, UV-Vis and IR spectra, and TGA analysis. X-ray structural analysis revealed that, oba and dpa ligands played an important role in the self-assembly of the helical chains by providing potential supramolecular recognition sites for π-π aromatic stacking and hydrogen-bond interactions, resulting in the self-assembly of the （4,4） networks to give a 3-D supramolecular framework. The photoluminescence properties of the title compound were also investigated, showing intense blue photoluminescence properties at room temperature.     

Supramolecular Architectures with Open Frameworks Constructed by Transitional Metal Ions,Linear Dicarboxylic Acid,and 2,2′‐Bipyridine

Four new transitional metal supramolecular architectures, [Zn(cca)(2,2′‐bpy)]_n · n(2,2′‐bpy) ( 1 ), [Cu(cca)(2,2′‐bpy)]_n ( 2 ), [Zn(bpdc)(2,2′‐bpy)(H₂O)]_n · 0.5nDMF · 1.5nH₂O ( 3 ), and [Co(bpdc)(2,2′‐bpy)(H₂O)]_n · nH₂O ( 4 ) (H₂cca = p‐carboxycinnamic acid; H₂bpdc = 4,4′‐biphenyldicarboxylic acid; 2,2′‐bpy = 2,2′‐bipyridine) were synthesized by hydrothermal reactions and characterized by single crystal X‐ray diffraction, elemental analyses, and IR spectroscopy. Although the metal ions in these four compounds are bridged by linear dicarboxylic acid into 1D infinite chains, there are different π–π stacking interactions between the chains, which results in the formation of different 3D supramolecular networks. Compound 1 is of a 3D open‐framework with free 2,2′‐bpy molecules in the channels, whereas compound 2 is of a complicated 3D supramolecular network. Compounds 3 and 4 are isostructural. Both compounds have open‐frameworks.     

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.     

Hydrothermal Synthesis of Five New Coordination Polymers Based on Benzophenone‐2, 4′‐dicarboxylic Acid and N‐Donor Spacers

Five new coordination polymers, namely, [Ni₂(L)₂(4, 4′‐bipy)₃)] · H₂O]_n ( 1 ), [Ni₂(L)₂(O) (bpp)₂]_n ( 2 ), [Zn(L)(bib)_0.5]_n ( 3 ), [Zn(L)(PyBIm)]_n ( 4 ), and [Zn₃(L)₂(OH)(im)]_n ( 5 ) [H₂L = benzophenone‐2, 4′‐dicarboxylic acid, 4, 4′‐bipy = 4, 4′‐bipyridine, bpp = 1, 3‐bis(4‐pyridyl)propane, PyBIm = 2‐(4‐pyridyl)benzimidazole, and im = imidazole] were synthesized under hydrothermal conditions. Structure determination revealed that compound 1 is a 3D network and exhibits a 4‐connected metal‐organic framework with (4².6³.8) topology, whereas compounds 2 , 3 , 4 , and 5 are two‐dimensional layer structures. In compounds 2 – 4 , dinuclear metal clusters are formed through carboxylic groups. In compound 5 , trinuclear metal clusters are formed through μ₃‐OH and carboxylic groups. The carboxylic groups exhibit three coordination modes in compounds 1 – 5 : monodentately, bidentate‐chelating, and bis‐monodentately. Furthermore, the luminescent properties for compounds 3 , 4 , and 5 were investigated.     

Synthesis,Structures, and Properties of two Helical Structures from Rigid Carboxylate Ligand and Flexible N‐Bridging Ligands

Two novel coordination polymers based on mixed ligands, [Zn(dpb)(bdc)(H₂O)]_n ( 1 ) and [Cd(dpb)(bbdc)(H₂O)(DMF)]_n ( 2 ) [dpb = 1, 4‐bis(pyridin‐3‐ylmethoxy)benzene, H₂bdc = 1, 4‐benzenedicarboxylate, H₂bbdc = 4, 4′‐dibenzenedicarboxylate], were synthesized under hydrothermal conditions. Compound 1 forms meso‐helical chain and shows three fold interpenetrating architecture with 4‐connected net {6 6} diamond topology. Compound 2 is a left‐ and right‐handed helical layer, which are interacted by π–π stacking interactions to construct a 3D framework. The luminescent properties of the compounds are discussed.     

Production and isolation of ligated metal(IV)‐oxo ions by tandem mass spectrometry

High valent metal(IV)‐oxo species, [M(?O)(MeIm)_n(OAc)]⁺ (M = Mn–Ni, MeIm = 1‐methylimidazole, n = 1–2), which are relevant to biology and oxidative catalysis, were produced and isolated in gas‐phase reactions of the metal(II) precursor ions [M(MeIm)_n(OAc)]⁺ (M = Mn–Zn, n = 1–3) with ozone. The precursor ions [M(MeIm)(OAc)]⁺ and [M(MeIm)₂(OAc)]⁺ were generated via collision‐induced dissociation of the corresponding [M(MeIm)₃(OAc)]⁺ ion. The dependence of ozone reactivity on metal and coordination number is discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Temperature Induced Interpenetration Suppression of a Couple of Azo‐based Isomers with a Flexible Second Ligand

Two new azo‐based coordination compounds with a flexible second ligand, crystal 1 (composed with [Zn(adc)(eda)]_n‐1) and crystal 2 (composed with {[Zn(adc)]_0.9568(eda)}_n‐1′ and {[Zn(adc)]_0.0414}_n) have been synthesized as a couple of isomers with different reaction temperature. Adc^2? and eda represent azobenzene‐4,4′‐dicarboxylic ion and 1,2‐ethanediamine, respectively. Single crystal X‐ray diffraction measurement indicates the interpenetration of the above crystals could be suppressed by simply tuning the reaction temperature, that is, the 5‐fold interpenetration which leads to no free volume left in lower temperature synthesized compound [Zn(adc)(eda)]_n‐1 could be reduced to a 4‐fold interpenetration in higher temperature synthesized {[Zn(adc)]_0.9568(eda)}_n‐1′ which results in free volume accounting for 3.6% (31.6 ų per unit cell volume) in crystal 2 . The synthesis, crystal structure and fluorescence spectra of crystals 1 and 2 have been discussed, together with the data of elemental analysis and X‐ray powder diffraction.     

Different Metal Aggregation in Copper Acetate Chain Coordination Polymers with Dipyridyl Tethers Bearing Hydrogen Bonding Capable Functional Groups

Hydrothermal synthesis has afforded a pair of divalent copper acetate coordination polymers containing either 4, 4′‐dipyridylamine (dpa) or 4‐pyridylisonicotinamide (4‐pina), both of which hydrogen‐bonding capable central functional groups. X‐ray crystallography revealed that both exhibit a 1D chain dimensionality. Use of the kinked tethering ligand dpa produced [Cu(OAc)₂(dpa)]_n ( 1 ), which possesses a simple chain based on dpa linkage of isolated copper ions. On the other hand, employing the straighter amide ligand 4‐pina generated {[Cu(OAc)₂(4‐pina)] · 0.5H₂O}_n ( 2 ), which exhibits {Cu₂O₂} rhomboid dimers formed through bridging acetate ligands. Weak antiferromagnetic coupling [g = 1.984(3), J = –3.2(3) cm^–1] was observed within the axial‐equatorial bridged {Cu₂O₂} dimers in 2 , with possible ferrimagnetism due to spin canting below 11 K.     

Syntheses,Crystal Structures,and Magnetic Properties of Two Cobalt Coordination Polymers Constructed From 1,3‐Bis(2,4‐dicarboxyphenyl) Benzene and Bis(imidazole) Linkers

Abstract. The 3D cobalt(II) coordination polymers [Co_1.5(HDDB)(1,4‐bib)_1.5(H₂O)]_n ( 1 ), and {[Co₂(DDB)(1,3‐bib)₂(μ₂‐H₂O)] · H₂O}_n ( 2 ) were assembled by mixed‐ligand synthetic strategy [H₄DDB = 1,3‐bis(2,4‐dicarboxyphenyl) benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and 1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene]. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. Single X‐ray diffraction analysis reveals that complex 1 is an interestingly 3D (3,3.6)‐connected (6³)₄(6⁵ · 8⁸ · 10²) net, and complex 2 is an unprecedented dinuclear [Co₂(COO)(μ₂‐H₂O)] SBUs based 3D (3,6)‐connected (3 · 6 · 7)(3² · 4³ · 5⁴ · 6³ · 7 · 8²) net. Additionally, the magnetic properties of 2 were investigated.     

Hydrothermal Syntheses and Characterizations of Three ZnII Coordination Polymers Tuned by pH Value and Base

Three new Zn^II coordination polymers, [Zn(bpe)(HL)₂(H₂O)]_n ( 1 ), {[Zn(bpe)(L)] · H₂O}_n ( 2 ), and [Zn₂Ca(bpe)(HL)₂(L)₂]_n ( 3 ) [H₂L = 5‐methoxyisophthalic acid and bpe = 1,2‐dis(4‐pyridyl) ethylene], were hydrothermally synthesized under different pH values and bases. Their structures were determined by single‐crystal X‐ray diffraction and further characterized by elemental analyses and IR spectroscopy. Polymer 1 is formed at pH = 4 and has a 1D chain structure. These 1D chains are linked by hydrogen bonds to afford a 1D double chain and further to form a threefold interpenetrating network. At pH = 7, a 2D layer structure of 2 with sql topology is formed. By using calcium hydroxide as base for the synthesis of 3 , a 3D network with pcu topology is obtained. These structural differences among 1 – 3 indicate that pH value and the identity of the base play important role in defining the overall structures of metal‐organic frameworks. In addition, the fluorescent properties of 1 – 3 are discussed.     

Synthesis,Structures and Properties of Four Coordination Polymers Constructed from 5‐Nitroisophthalate and Benzimidazole Ligand

Four coordination polymers, [Cu(NIPH)(Bim)₂]_n ( 1 ), [Co(NIPH)(Bim)₂]_n ( 2 ), [Zn(NIPH)(Bim)]_n ( 3 ), and [Cd(NIPH)(Bim)(H₂O)]_n ( 4 ) (NIPH = 5‐nitroisophthalate and Bim = benzimidazole) have been synthesized and characterized by elemental analysis, IR, TGA and single‐crystal X‐ray diffraction. The crystal structural analyses reveal that 1 and 2 are composed of zig‐zag chains and straight line chains, respectively. 3 and 4 are constructed by double‐stranded loop‐like chains. All these chain‐like structures are finally packed into three‐dimensional networks through hydrogen bonds. Thermogravimetic analyses (TGA) of 1 – 4 and temperature‐dependent magnetic susceptibilities of 1 have been performed.     

Syntheses and Crystal Structures of a Series of Coordination Polymers Constructed From C2‐Symmetric Ligand 1,3‐Adamantanedicarboxylic Acid

This article systematically investigates the influence of the properties of inhomogeneous N‐auxiliary ligands and pH value on the helical structures of complexes based on C₂‐symmetric ligand 1,3‐adamantanedicarboxylic acid (H₂ADC). Five kinds of neutral ligands (phen=1,10‐phenanthroline, bipy=4,4′‐bipyridine, bpa=1,2‐bis(4‐pyridyl)ethane, bpe=1,2‐bis(4‐pyridyl)ethane, and bpp=1,3‐bis(4‐pyridyl)propane) were selected, and a series of new Zn^II/Co^II dicarboxylates have been synthesized by slow diffusion, namely, [Zn(phen)(ADC)(H₂O)]₂ ? CH₃OH ( 1 ), {[Zn(ADC)(bpe)] ? H₂O}_n ( 2 ), {[Zn(ADC)(bipy)] ? 2 H₂O}_n ( 3 ), {[Zn(ADC)(bpa)]₂ ? 5 H₂O}_n ( 4 ), {[Zn(ADC)(bpp)]₂ ? CH₃OH}_n ( 5 ), {[Zn(ADC)(bpp)]}_n ( 6 ), {[Co(ADC)(bpp)(CH₃OH)(H₂O)] ? CH₃OH ? 2 H₂O}_n ( 7 ), and {[Co(ADC)(bpp)]}_n ( 8 ). Single‐crystal X‐ray structural analysis shows that complex 1 forms a 0D dinuclear with closed‐loop unit. The complex 2 is a 2D layer framework. Compounds 3 and 4 are isomorphous with a small discrepancy and present one‐dimensional chainlike structures. It is interesting that the 2D organic–inorganic hybrid frameworks containing meso‐helical chains have been observed. Compound 5 is a 2D interpenetrated network with (4,4) topology, in which homochiral left‐handed helical chains are arranged in an ABAB sequence parallel to the plane defined by (a,c), and right‐handed helical chains running along the a axis are also observed in the solid state, resulting in a meso‐helical structure. Compounds 6 , 7 , and 8 crystallize in a chiral space group P212121. Highly dimensional 6 and 8 are essentially isostructural and present a threefold interpenetrated 3D diamondoid network containing three helical chains, whereas 7 exhibits a 2D grid layer with a left‐handed helical chain. Furthermore, thermal stability, X‐ray powder diffraction, and the luminescent properties of 1 , 2 , 3 , 4 , 5 , 6 are also discussed.     

Coordination Frameworks based on 3,5‐Bis(imidazole‐1‐yl)­pyridine and Aromatic Dicarboxylate Ligands: Synthesis,Crystal Structures,and Photoluminescent Properties

Three metal coordination polymers [Zn(bdc)(L)(H₂O)]_n ( 1 ), [Co(pta)(L)(H₂O)₂]_n ( 2 ), and [Cd(tda)(L)(H₂O)]_n ( 3 ) [H₂bdc = 1,2‐benzene dicarboxylate acid, H₂pta = terephthalic acid, H₂tda = 2,5‐thiophenedicarboxylic acid, L = 3,5‐bis(imidazole‐1‐yl)pyridine] were synthesized and structurally characterized by IR spectroscopy, elemental analysis, X‐ray powder diffraction, and X‐ray single crystal diffraction. Complex 1 shows a three‐dimensional (3D) structure with cco topology with the symbol 6⁵ · 8, whereas complex 2 features a 3D structure with cds topology with the symbol 6⁵ · 8. Complex 3 has a 2D network constructed by the cadmium atoms bridged through the ligands tda and L. Their X‐ray powder diffraction patterns were compared with the simulated ones. Moreover, their luminescent properties were investigated in the solid state at room temperature, and the thermogravimetric analyses were carried out to study the thermal stability of the 3D networks.     

Coordination compounds of nickel with trithiocyanuric acid. Part IV. Structure of [Ni(pmdien)(ttcH)] (pmdien = N,N,N′,N′,N′′-pentamethyldiethylenetriamine,ttcH3 = trithiocyanuric acid)

Ni^II mixed-ligand complexes of compositions [Ni(pmdien)(ttcH)] (1), [Ni(baphen)₂(ttcH)] · 4H₂O (2), [Ni-(dpa)(ttcH)(H₂O)] (3), [Ni(cyclam)(ttcH)] · 2H₂O (4), [Ni(hexaa)](ttcH) (5) and [Ni(hexab)(ttcH)] · 2H₂O (6), (baphen = 4,7-diphenyl-1,10-phenanthroline, dpa = 2,2-dipyridylamine, cyclam = 1,4,8,11-tetraazacyclotetradecane, hexaa = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1^6,9]-octadecane, hexab = 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane) have been prepared and characterized by means of i.r., u.v.–vis. spectroscopies and magnetochemical measurements. The redox properties of the complexes were studied by cyclic voltammetry. The crystal and molecular structure of [Ni(pmdien)(ttcH)] was determined. The nickel atom is penta-coordinated by three N atoms of pmdien, and by S and N atoms of trithiocyanurate(2–) anion.     

Two Zinc(II) Coordination Polymers Based on Terphenyl‐2,2′,4,4′‐tetracarboxylate and Dipyridyl Ligands: Syntheses,Crystal Structures,and Luminescent Properties

Two coordination polymers, {[Zn₂(L)(bpy)] · 2H₂O}_n ( 1 ) and [Zn₂(L)(bpe)]_n ( 2 ) [H₄L = terphenyl‐2,2′,4,4′‐tetracarboxylic acid, bpy = 4,4′‐bipyridine, and bpe = 1,2‐bis(4‐pyridyl)ethane], were hydrothermally synthesized under similar conditions and characterized by elemental analysis, IR spectroscopy, TGA, and single‐crystal X‐ray diffraction analysis. Compound 1 has a 3D framework containing Zn–O–C–O–Zn 1D chains. Compound 2 exhibits a 3D framework, which features tubular channels. The channels are occupied by bpe molecules. The differences in the structures demonstrate that the auxiliary dipyridyl‐containing ligand has a significant effect on the construction of the final framework. Additionally, the fluorescent properties of the two compounds were also studied in the solid state at room temperature.     

Syntheses,Crystal Structures,and Photocatalytic Activities of Three Copper Coordination Polymers Based on Bis(1H‐imidazol‐4‐yl)benzene/3‐(2‐Pyridyl)pyrazole

Three copper(II) coordination polymers (CuCPs), namely, [Cu_0.5(1,4‐bib)(SO₄)_0.5]_n ( 1 ), {[Cu(1,3‐bib)₂(H₂O)] · SO₄ · H₂O}_n ( 2 ), and [Cu(bpz)(SO₄)_0.5]_n ( 3 ), were assembled from the reaction of three N‐donors [1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and Hbpz = 3‐(2‐pyridyl)pyrazole] with copper sulfate under hydrothermal conditions. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric analyses (TGA). Structure analyses reveal that complex 1 is a 3D 6‐connected {4¹² · 6³}‐ pcu net, complex 2 is a fourfold 3D 4‐connected 6⁶‐ dia net, whereas complex 3 is a 1D snake‐like chain, which further expanded into 3D supramolecular architectures with the help of C–H ··· O hydrogen bonds. Moreover, the photocatalytic tests demonstrate that the obtained CuCPs are photocatalysts in the degradation of MB with the efficiency is 86.4 % for 1 , 75.3 % for 2 , and 91.3 % for 3 after 2 h, respectively.     

Syntheses,Crystal Structures,and Magnetic Properties of Three 1D Chain Metal–Nitroxide Complexes Bridged by ­Flexible Dicarboxylate Anions

Three new one‐dimensional (1D) chain metal–nitroxide complexes {[Cu(NIT4Py)₂(suc)(H₂O)] · 3H₂O}_n ( 1 ), {[Cd(NIT4Py)₂(suc)(H₂O)] · [Cd(NIT4Py)₂(suc)(H₂O)₂] · 3H₂O}_n ( 2 ), and {[Zn(NIT4Py)(glu)(H₂O)] · H₂O}_n ( 3 ) [NIT4Py = 2‐(4′‐pyridyl)‐4, 4, 5, 5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide, suc = succinate anion and glu = glutarate anion] were synthesized and structurally characterized. Single‐crystal X‐ray analyses indicate that the three complexes crystallize in neutral 1D chains in which the metal‐nitroxide units are linked by flexible dicarboxylate anions. The succinate anions only adopt trans configuration in complexes 1 and 2 , whereas the glutarate anion has gauche/anti conformation in complex 3 . Magnetic measurements show that complex 1 exhibits weak antiferromagnetic interactions between the copper ions and the nitroxides.