Three-dimensional Coordination Framework Research Articles

A new three-dimensional coordination polymer of Sr(II) based on dipicolinic acid, with different coordination environments for Sr(II).

A three-dimensional coordination polymer of Sr(II) based on dipicolinic acid (pydcH2) has been synthesized and characterized, namely poly[[diaquabis(μ3-6-carboxypyridine-2-carboxylato)bis(μ4-pyridine-2,6-dicarboxylato)tristrontium(II)] dihydrate], {[Sr3(C7H3NO4)2(C7H4NO4)2(H2O)2]·2H2O}n. The asymmetric unit consists of two unique Sr(II) centres (one of them situated on an inversion centre), two independent pydc(2-) ligands, and one coordinated and one uncoordinated water molecule. The two independent Sr(II) cations are surrounded by water and dipicolinate molecules in distorted square-antiprism and distorted tricapped trigonal prismatic geometries. The dipicolinate ligands adopt μ3- and μ4-bridging modes, linking the alkaline earth metal centres into a three-dimensional coordination framework. One dipicolinate ligand is doubly deprotonated, while the other is singly deprotonated.

Flexible Bis(imidazole) Mediated Assembly of Silver(I)–Organic Frameworks with Ethynide and Trifluoroacetate Ligands

A new family of 10 organosilver(I) complexes, namely, [(AgC≡CPh)2(AgO2CCF3)4(cis-1,2-bix)(CH3OH)]·2CH3OH (1,2-bix = 1,2-bis(imidazol-1-ylmethyl)benzene, 1A), [(AgC≡CC6H4Me-2)2(AgO2CCF3)4(cis-1,3-bix)]·5.25H2O (1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene, 1B), [(AgC≡CPh)3(AgO2CCF3)6(trans-1,4-bix)(CH3OH)3]·2CH3OH (1,4-bix = 1,4-bis(imidazol-1-ylmethyl)benzene, 2A), [(AgC≡CC6H4Me-4)3(AgO2CCF3)6(trans-1,4-bix)(CH3OH)3]·2CH3OH (2B), [(AgC≡CPh)(AgO2CCF3)3(trans-1,3-bix)(H2O)]·0.5H2O (3A), [(AgC≡CC6H4Me-4)(AgO2CCF3)3(trans-1,3-bix)(H2O)] (3B), [(AgC≡CC6H4Me-4)(AgO2CCF3)3(bbi)(H2O)] (bbi = 1,1′-(1,4-butanediyl)bis(imidazole), 3C), [(AgC≡CC6H4tBu-4)(AgO2CCF3)3(trans-1,4-bix)] (3D), [(AgC≡CPh)2(AgO2CCF3)4(bbi)(H2O)]·2H2O (4), and [(AgC≡CtBu)2(AgO2CCF3)4(bbi)] (5), have been synthesized employing a variable combination of ethynide, trifluoroacetate, and bridging bis(imidazole) ligands. In both 1A and 1B, the flexible 1,2-bix or 1,3-bix ligands in cis-conformations are alternatively attached on both sides of an infinite cationic silver(I) chain, and neighboring organosilver(I) chains are further interconnected by intermolecular hydrogen bonds to generate a three-dimensional supramolecular architecture. In structural analogues 2A and 2B, pairs of silver(I) chains are linked via the trans-1,4-bix ligands to yield infinite ladders, which are further joined together by hydrogen bonds to afford a three-dimensional supramolecular network. In the isostructural series 3A–3D, centrosymmetric (PhC2)2Ag8 aggregates are connected by trifluoroacetate groups to give an infinite chain, and such chains are then bridged by bis(imidazole) ligands to generate a coordination layer. Furthermore, adjacent layers are linked by hydrogen bonds to form a three-dimensional supramolecular network. In 4, infinite silver(I)–phenylethynide chains constructed by Ag6 aggregates are bridged by bbi ligands in a gauche–trans–gauche conformation to yield a three-dimensional coordination framework. In contrast, infinite silver(I)-tert-butylethynide chains based on Ag8 and Ag6 aggregates in 5 are linked by bbi ligands exhibiting different trans–trans–trans and gauche–trans–gauche conformations to generate a three-dimensional coordination network. Finally, the roles played by various bis(imidazole) ligands and ethynides bearing different substituents in the framework assembly are discussed in detail.

Hydrothermal Synthesis, Crystal Structure, and Luminescence Property of an Mn-Tb Complex Based on 5-(isonicotinamido)-isophthalate

A 3d-4f heterometallic coordination polymer, [Mn0.5Tb (INAIP)2(H2O)2]·2H2O (1) has been prepared by hydrothermal reactions of the corresponding lanthanide salt with 5-(isonicotinamido)isophthalic acid (H2INAIP) in the presence of MnSO4·H2O and NaOH. X-ray single-crystal structural analysis reveals that 1 features non-interpenetrated three-dimensional (3D) coordination framework containing two-dimensional (2D) (4, 4) Tb-carboxylate layers. In addition, 1 also displayed photoluminescent properties in the green range at room temperature.

Porous coordination polymers based on functionalized Schiff base linkers: enhanced CO2uptake by pore surface modification

We report the synthesis, structural characterization and adsorption properties of three new porous coordination polymers {[Cu(Meazpy)0.5(glut)](H2O)}n (2), {[Zn(azpy)0.5(terep)](H2O)}n (3), and {[Zn(Meazpy)0.5(terep)]}n (4) [glut = glutarate, terep = terephthalate, azpy = N,N'-bis-(pyridin-4-ylmethylene)hydrazine and Meazpy = N,N'-bis-(1-pyridin-4-ylethylidene)hydrazine] composed of mixed linkers systems. Structure determination reveals that all three compounds have three-dimensional (3D) coordination frameworks bridged by dicarboxylates and Schiff base linkers. In all cases 2D dicarboxylate layers are supported by paddle-wheel M2(CO2)4 SBUs extended in three dimensions by designed Schiff base linkers. Compound 1, which has been reported in a paper earlier by our group, is a robust porous three-dimensional (3D) framework whose pore surface was found to be decorated with the -CH=N- groups of a linear Schiff base (azpy) and it showed reversible single-crystal-to-single-crystal transformation and selective CO2 uptake. By using another linear Schiff base linker Meazpy, we have synthesized compound 2 which is isostructural with 1, having an additional methyl group pointing towards the pore. Like 1 it also shows a reversible single-crystal-to-single-crystal transformation upon dehydration and rehydration. The dehydrated framework of 2 exhibits 50% enhanced CO2 uptake compared to 1. This has been achieved by the pore surface modification effected upon changing the pillar backbone from a -CH=N- to -CMe=N- group. It also adsorbs water vapour at 298 K. In the case of the two isostructural 3D MOFs 3and 4, the use of a rigid carboxylate (terephthalate) linker arrested porosity by three-fold interpenetration. We showed that the use of aliphatic dicarboxylate (glutarate) results in a non-interpenetrated framework rather than the common interpenetrated framework with aromatic dicarboxylates in mixed ligand systems.

Construction of silver–organic framework with silver rods of repeated Ag-triangle units: Synthesis, structure, and properties

Abstract A new thick silver rod incorporating repeated Ag3 units sustained by 1,3,5-benzenetricarboxylic acid (1,3,5-H3BTC) and Ag⋯Ag interactions, {[Ag3(BTC)(pyz)]·(H2O)}n (1) (pyz = pyrazine), has been synthesized and structurally characterized. Compound 1 displays a three-dimensional coordination framework with infinite 1D Ag rod, and adjacent silver rods bridged by the 1,3,5-H3BTC and pyz ligand. Argentophilicity plays an important role in determining the infinite silver(I) rods. Complex 1 exhibits photoluminescence maximized at 542 nm upon 363 nm excitation at room temperature, which may be mainly assigned to ligand-to-metal charge transfer (LMCT) perturbed by Ag⋯Ag interactions. Temperature dependent luminescence spectra from 298 to 77 K have been studied. Upon decreasing the temperature from 298 to 77 K, the emission bands grow in intensity. In addition, the thermogravimetric analysis and powder X-ray diffraction (PXRD) of complex 1 have also been investigated.

In situ hydrothermal syntheses of five new cadmium(ii) coordination polymers based on 3-(1H-tetrazol-5-yl)benzoate ligand

Five new cadmium(II) tetrazole-based compounds, {[Cd4(3-tzba)4(H2O)2]·2H2O (1), [Cd(3-tzba)(2,2′-bipy)2] (2), [Cd(3-tzba)(1,10-phen)] (3), [Cd3(3-tzba)2(NA)2(H2O)] (4) and [Cd(3-tzba)(BIO)] (5), where 3-tzba = 3-(1H-tetrazol-5-yl)benzoate, 2,2′-bipy = 2,2′-bipyridine, 1,10-phen = 1,10-phenanthroline, NA = nicotinic acid, BIO = benzo-biimidazolediones}, were successfully synthesized involving the in situ generation of ligand under hydrothermal conditions. The compounds were thoroughly characterized by elemental analyses, Fourier transform infrared spectroscopy, thermal studies, and single crystal and powder X-ray diffraction. Compound 1 represents a three-dimensional (3D) coordination framework built up by the assembly of two-dimensional (2D) Cd-3-tzba wheel layers and 3-tzba linkers, exhibiting a pcu (412·63) topological net. Compound 2 displays a one-dimensional (1D) zigzag chain formed by the linkage of Cd(II) centers and 3-tzba ligands. Compound 3 shows a 1D pearl-necklace-like chain built by the interconnection of Cd(II) centers and 3-tzba ligands. Compound 4 is a 3D coordination framework which is constructed by 1D [Cd3] chains with 3-tzba and NA ligands linkers displaying a hxl (36) type net. Compound 5 exhibits a 3D sql (44) topological network, with 1D Cd chains linking the adjacent 3-tzba and BIO ligands. It is noted that the 3-tzba and BIO ligands are generated in situ from the precursor 3-cyanobenzoic acid and 1,2,4,5-benzenetetracarboxylic acid (H4bta), respectively. In addition, the luminescent properties of these compounds were investigated.

Synthesis and structure of coordination polymers of Mn2+, Cu2+, Ag+, Zn2+ and Cd2+ by combination of bipyrazole and diphenate ligands

Five new coordination polymers, [Mn(DPA)(Me4bpz)(H2O)](I)∞1, [Cu(DPA)(Me4bpz)2]·H2O(II)∞1, [Ag4(OAc)2(Me4bpz)3(H2O)1.56](III)∞2, [Zn(DPA)(Me4bpz)]·0.61H2O(IV)∞3 and [Cd(DPA)(Me4bpz)](V)∞3[DPA: diphenic acid dianion, OAc: acetate, Me4bpz: 3,3′,5,5′-tetramethyl-4,4′-bipyrazole], were obtained from acetate hydrates of Mn2+, Cu2+, Ag+, Zn2+ and Cd2+ and a mixed ligand system consisting of Me4bpz and diphenic acid by hydrothermal synthesis under similar conditions. Their crystal structures were determined by means of X-ray single crystal structure analysis. Furthermore, the compounds were characterized by means of elemental analysis and IR spectroscopy. The polymers I and II exhibit one-dimensional chain structures with only one type of bridging ligand, whereas the polymers IV and V realize three-dimensional coordination frameworks with diamond topology involving both ligand types as bridging ligands. Compound III contains a two-dimensional cationic framework which is charge compensated by acetate anions. The coordination environments of the metal centers are predominant directly supported by N–H⋯O hydrogen bonds providing further evidence for the bipyrazole-carboxylate supramolecular synthon.

Assembly of Silver-Organic Frameworks and Discrete Molecules Containing Embedded 1,3-Butadiyne-1,4-diide with Ancillary Heteroaromatic N-Donor Ligands

Six new silver(I) double salts containing embedded 1,3-butadiyne-1,4-diide (C42–) and various types of ancillary heteroaromatic N-donor ligands, namely [{(Ag2C4)0.5(AgNO3)3(L1)}·H2O]n (1; L1 = 3-chloropyridine), [(Ag2C4)2(AgCF3CO2)9(L1)7(H2O)]n (2; L1 = 3-chloropyridine), [(Ag2C4)2(AgCF3CO2)9(L2)7(H2O)]n (3; L2 = 3-bromopyridine), [{(Ag2C4)(AgCF3CO2)5(L3)1.5(H2O)2}·H2O]n (4; L3 = 2-methylpyrazine), [(Ag2C4)(AgCF3CO2)6(L4)6] (5; L4 = 2-cyanopyridine), and [(Ag2C4)(AgCF3CO2)10(L5)8] (6; L5 = imidazole) have been synthesized and characterized by X-ray crystallography. Complex 1 exhibits a two-dimensional coordination network in which the basic building unit is a [Ag4C4Ag4] aggregate. Isomorphous complexes 2 and 3 feature a composite-chain structure with trifluoroacetate and halogen-substituted pyridine ligands surrounding a columnar silver backbone. Complex 4 is a three-dimensional coordination framework composed of silver columns cross-linked by external silver atoms and 2-methylpyrazine bridges. Complex 5 ...

Structures and magnetism of metal(II) compounds with mixed azide and carboxylate bridges derived from zwitterionic dicarboxylate ligands

Three coordination polymers of different transition metal ions with azide and flexible zwitterionic dicarboxylate ligand 1-carboxymethylpyridinium-4-benzoate (L) were synthesized and structurally and magnetically characterized. They are formulated as [M(L)(N3)]·H2O (M=Co, 1 and Ni, 2) and [Cu3(L)2(N3)4]·7H2O (3). In the isomorphous compounds 1 and 2, neighboring metal ions are linked by mixed triple (μ-EO-N3)(μ-COO)2 bridges to give an anionic chain of [M(N3)(COO)2]n, and each chain is cross-linked by the cationic 1-methylpyridinium-4-phenyl spacers to give a two-dimensional coordination layer. Magnetic studies demonstrated that the triple bridge transmits intrachain ferromagnetic interactions but show different bulk properties: compound 1 diplays a new SCM-based material exhibiting antiferromagnetic ordering, metamagnetic transition, and field-modulated slow dynamics, while compound 2 shows the usual one-dimensional ferromagnetism. Compound 3 consists of three-dimensional coordination framework in which Cu(II) chains with alternating double (μ-EO-N3)2 bridges and triple (μ-EO-N3)(μ-COO)(μ-Ocarboxylate) bridges are interlinked by the organic spacer. Magnetic studies suggested that ferromagnetic interactions between the neighboring Cu(II) ions through the alternating bridges.

A 3-D Metal-Organic Framework Constructed with Manganese(ΙΙ), 4,4'-Oxybis(benzoic acid) and 2,2'-Biphenyl: Synthesis, Crystal Structure and Photoelectric Property Characterization

Assembly of 4,4'-oxybis(benzoic acid) (H2L) with manganese chloride in the presence of 2,2'-biphenyl (2,2'-bpy) affords a new coordination polymer [Mn3L3(2,2'-bpy)2]n (1), in which the [MnL2]n layers are extended by L bridges resulting in a three-dimensional (3-D) coordination framework. The network structure of 1 has unusual (2,6)-connectivity and represents a new type of (812·123)(8)(3) topology. These identical and complementary networks are entangled to generate a self-penetrating supramolecular lattice. Moreover, the fluorescence spectrum of 1 exhibits fluorescent emission in the solution of methanol at room temperature. Electrochemical investigation illustrates the electrochemical properties of the title compound. The structure (C62H40Mn3N4O15)n is monoclinic with a = 14.2304(18), b = 17.019(2), c = 25.805(3) Å, α = γ = 90, β = 92.932(2)° and space group C2/c.

A novel three-dimensional CdIIcoordination polymer: poly[[aquabis(2,2′-bipyridine)(μ5-pyrazol-1-ide-3,5-dicarboxylato)(μ4-pyrazol-1-ide-3,5-dicarboxylato)(μ3-pyrazole-3,5-dicarboxylato)tetracadmium(II)] dihydrate

The title compound, {[Cd(4)(C(5)H(2)N(2)O(4))(C(5)HN(2)O(4))(2)(C(10)H(8)N(2))(2)(H(2)O)]·2H(2)O}(n), crystallized in the monoclinic space group P2(1)/n and displays a three-dimensional architecture. The asymmetric unit is composed of four crystallographically independent Cd(II) centres, two triply deprotonated pyrazole-3,5-dicarboxylic acid molecules, one doubly deprotonated pyrazole-3,5-dicarboxylic acid molecule, two 2,2'-bipyridine ligands, one coordinated water molecule and two interstitial water molecules. Interestingly, the Cd(II) centers exhibit two different coordination numbers. Two Cd(II) centres adopt a distorted octahedral arrangement and a third a trigonal-prismatic geometry, though they are all hexacoordinated. However, the fourth Cd(II) center is heptacoordinated and displays a pentagonal-bipyramidal geometry. The three anionic ligands adopt μ(3)-, μ(4)- and μ(5)-bridging modes, first linking Cd(II) centers into a one-dimensional wave-like band, then into a wave-like layer and finally into a three-dimensional coordination framework, which is stabilized by hydrogen bonds.

Simple One-Pot Preparation of In2O3 Nano-particles Using a Supramolecular 3D Framework Polymer

An indium(III) three-dimensional coordination framework, [In2(OH)3(O4C8H4)1.5] n (1), was synthesized by hydrothermal method and characterized by elemental analyses, X-ray powder diffraction (XRD) and IR spectroscopy. Indium(III) oxide nanoparticles was prepared by direct thermal decomposition of 1 at 450 °C in air. The indium(III) oxide nanoparticles were characterized by scanning electron microscopy, X-ray powder diffraction (XRD) and energy-dispersive X-ray analysis (EDAX). This study demonstrates the coordination polymer frameworks may be suitable precursors for a simple one-pot preparation of nanoscale metal oxide materials with different and interesting morphologies.

Three-dimensional 3d-4f heterometallic coordination polymers: syntheses, structures and properties

Six new 3d-4f heterometallic coordination polymers, {[Ln4Cu2(INAIP)8(H2O)15]·14H2O}n [Ln = La (1), Pr (2), Nd (3)] and {[LnCo0.5(INAIP)2(H2O)2]·2H2O}n [Ln = Tb (4), Dy (5), Yb (6), H2INAIP = 5-(isonicotinamido)isophthalic acid] have been synthesised and characterised by single crystal X-ray diffraction analysis. The results of structural analyses showed that 1–3 are isomorphous showing two-fold interpenetrated three-dimensional (3D) coordination framework, while 4–6 have the same non-interpenetrated 3D structure with 2D (4, 4) lanthanide-carboxylate layers. The results revealed that the different transition metal centres have great influence on the structures of the resulted complexes in this system. In addition, thermogravimetric and magnetic properties of 1–6, and photoluminescence of 4 were investigated.

Copper(ii) and nickel(ii) coordination polymers assembled from 2,4-dibenzoylisophthalic acid and different N-donor co-ligands: syntheses, crystal structures, and magnetic properties

Four new coordination polymers based on 2,4-dibenzoylisophthalic acid and different N-donor auxiliary co-ligands, {Cu2L2(4,4′-bpy)}n (1), {Ni2L2(4,4′-bpy)}n (2), {[Cu10(L)8(bbi)(μ3–OH)4(H2O)6]·4H2O}n (3) and {[CuL(bth)(H2O)]·H2O}n (4) (H2L = 2,4-dibenzoylisophthalic acid, 4,4′-bpy = 4,4′-bipyridine, bbi = 1,1′-(1,4-butanediyl)bis(imidazole) and bth = 1,6-bis(1,2,4-triazol-1-yl)hexane), have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-Vis spectra, powder X-ray diffraction and thermogravimetric analysis. Complexes 1 and 2 are isostructural and crystallized in the chiral space groupP3221. They both possess three-dimensional (3D) coordination frameworks with 6-connected (44·510·7) topology that are incorporated left-handed helices and right-handed double helices substructures based on M(II) (M = Cu, Ni) paddle-wheel clusters. Complex 3 exhibits a 3D (4,5)-connected network with (44·62) (44·66) topology, in which dinuclear Cu2(CO2)4 clusters act as 4-connected nodes and tetranuclear [Cu4(μ3–OH)2]6+clusters serve as 5-connected nodes. Complex 4 shows a two-dimensional (2D) parallelogrammic network with (4,4) topology. The magnetic properties for 1–3 have been investigated and exhibited antiferromagnetic interaction.

Ag(i) and Zn(ii) coordination polymers with a bulky naphthalene-based dicarboxyl tecton and different 4,4′-bipyridyl-like bridging co-ligands: structural regulation and properties

A series of six Ag(I) and Zn(II) coordination polymers, namely, [Ag(2)(ndc)](∞) (1), {[Zn(ndc)(H(2)O)](H(2)O)}(∞) (2), {[Ag(2)(ndc)(4bpy)(2)][Ag(4bpy)(H(2)O)](ClO(4))(H(2)O)(2)}(∞) (3), [Zn(5)(ndc)(4)(4bpy)(2)(μ(3)-OH)(2)](∞) (4), {[Ag(ndc)(abp)][Ag(abp)](H(2)O)(3)}(∞) (5), and {[Zn(2)(ndc)(2)(abp)(H(2)O)(2)](H(2)O)(2)}(∞) (6), have been prepared by using 2,3-naphthalenedicarboxylic acid (H(2)ndc), an analogue of 1,2-benzenedicarboxylic acid (H(2)bdc), and different 4,4'-bipyridyl-like bridging co-ligands 4,4'-bipyridine (4bpy) and trans-4,4'-azobis(pyridine) (abp). The initial complexes 1 and 2 display the unusual two-dimensional (2-D) five-connected (4(8).6(2)) and the 2-D three-connected (4.8(2)) coordination networks, respectively. When two comparable rod-like linkers 4bpy and abp (with different N,N'-donor separations of the molecular backbones of ca. 7 and 9 Å) are further introduced, two one-dimensional (1-D) complexes 3 and 5, a three-dimensional (3-D) coordination framework 4 with (4(3))(4(3).6(3))(4(3).6(5).8(2))(4(4).6(4).8(2))(4(10).6(5)) topology and a 2-D 6(3) layered coordination polymer 6 are constructed. A structural comparison of these complexes with those based on the structurally related bdc ligand suggests that the extended π-conjugated system of ndc with different electronic nature and steric bulk play an important role in constructing the supramolecular architectures for 1-6, which are also regulated by different bridging N-donor co-ligands and metal ions. Moreover, complexes 1-6 show strong solid-state luminescence emissions at room temperature that mainly originate from the intraligand transitions of ndc.

Homochiral transition-metal camphorate coordination architectures containing “piperazine–pyridine” ligands

A total of five homochiral metal–organic coordination polymers (MOCPs) showing high thermal stability have been assembled from the reaction of divalent transition-metal ions (Co2+, Zn2+, and Cd2+), rigid enantiopure D-camphoric acid (D-H2Cam), and achiral neutral N,N′-bis(pyrid-4-yl)piperazine (bpypip) ligand under hydro(solvo)thermal conditions. Compound [Co2(D-Cam)2(bpypip)] (1) features a chiral-layered cobalt–camphorate coordination (4,4)-net, which is pillared by auxiliary linear N-tethering bpypip linkers to yield a homochiral three-dimensional coordination framework with Schlafli symbol of 44·610·8. Compounds [M(D-HCam)2(bpypip)] (2, M = Cd; 3, M = Zn) have nearly identical one-dimensional M–bpypip zigzag coordination-chain structures, in which each metal ion further attaches to two partially deprotonated monoanionic D-HCam terminals, which exhibit two types of partially deprotonating manner in 2 but only one type in 3. Through chain-to-chain C(O)OH⋯O(carboxylate) hydrogen bonds, the zigzag coordination-chain becomes extended to a three-dimensional uninodal 6-connected supramolecular network, which can be considered as a result of a M–D-HCam-based 4-connected supramolecular 65·8-net intersected by M–bpypip-based zigzag coordination-chains. Of particular interest, the supramolecular assembly contains a couple of single-stranded right- (SRH) and left-handed (SLH) supramolecular helices and a couple of double-stranded right- (DRH) and left-handed (DLH) supramolecular helices, and therefore exists as a meso-net in topology, i.e., there is no spatial chirality. Compounds [M2(OH)(OAc)(D-Cam)(bpypip)] (4, M = Co; 5, M = Zn) have identically homochiral ladder-like chain structures having meso-M2 units and presenting three kinds of different anions, i.e., hydroxyl, acetate, and D-Cam. The obtained acetate anion may be generated from the hydrolyzation of dimethylacetamide (DMAc) under hydro(solvo)thermal conditions.

Solvothermal synthesis, structure and properties of a new 3-D anionic porous framework

A new three-dimensional porous Zinc(II) metal-organic framework [NH 2 Et 2 ][Zn(BTC)]·H 2 O ( 1 ) was synthesized by the self-assembly of 1,3,5-benzenetricarboxy acid (H 3 BTC) and Zn(II) salt in diethylformamide (DEF), and characterized by single-crystal X-ray structure determination, thermogravimetric analysis and X-ray powder diffraction studies. The adsorption behavior shows that compound 1 has selective adsorption capacities of CO 2 over N 2 after the removal of the water molecules within the pores. A novel 3D Zn(II) coordination polymer, [NH 2 Et 2 ][Zn(BTC)]·0.5H 2 O ( 1 ) [BTC = 1,3,5-benzenetricarboxylate], has been solvothermally synthesized and characterized. Complex 1 shows a rare rtl topology net with selective adsorption capacities of CO 2 over N 2 . ► Three-dimensional anionic coordination framework. ► Solvothermal synthesis effect on formation and structure of the anionic metal-organic framework. ► Selective sorption behavior of CO 2 over N 2 .

New Polyoxometalate Species Stabilized in Coordination Networks Constructed with the Multinuclear Silver(I) Ethynediide Aggregate C2@Agn (n = 6 and 7)

Three polyoxometalate-based silver(I) ethynediide complexes have been obtained by hydrothermal synthesis. New types of polyoxometalate motifs are generated and stabilized in a silver-rich environment in their respective three-dimensional coordination frameworks via assembly of the polyhedral metal-ligand C(2)@Ag(n) (n = 6 and 7) supramolecular synthon.

Poly[diaqua(μ2-5-carboxypyridine-3-carboxylato-κ2N:O3)hemi(μ2-oxalato-κ4O1,O2:O1′,O2′)(μ4-pyridine-3,5-dicarboxylato-κ4N:O3:O3′:O5)silver(I)terbium(III)

In the title coordination polymer, [AgTb(C7H3NO4)(C7H4NO4)(C2O4)0.5(H2O)2]n, the TbIII ion is eight-coordinated by three O atoms from three different pydc (H2pydc = pyridine-3,5-dicarboxylic acid) ligands, one O atom from one Hpydc ligand, two O atoms from one oxalate ligand and two water mol­ecules in a distorted square-anti­prismatic geometry. The AgI ion is coordinated in an almost linear fashion by two pyridyl N atoms from one pydc and one Hpydc ligand and has weak inter­actions with two carboxyl­ate O atoms. The carboxyl­ate groups of pydc and Hpydc ligands link Tb centers, forming a one-dimensional chain. The oxalate adopts a tetra­dentate bis-chelating coordination mode, connecting the chains into a two-dimensional layer. These layers are further assembled via [Ag(pydc)(Hpydc)] pillars and O—H⋯O and C—H⋯O hydrogen bonds into a three-dimensional coordination framework.

Two rod-based 3-D lead(II) tetrafluoroterephthalate coordination frameworks with sra topology: Syntheses, structures, and properties

Abstract Two three-dimensional (3-D) PbII coordination frameworks [Pb(BDC-F4)(CH3OH)]n (1) and [Pb(BDC-F4)(DMF)(CH3OH)]n (2) have been prepared by the reactions of Pb(NO3)2 with a rigid dicarboxyl compound tetrafluoroterephthalic acid (H2BDC-F4) in different solvents. Single crystal X-ray diffraction reveals that both complexes show the unusual rod-based coordination networks with sra topology, although they crystallize in different space groups (C2/c and P 1 ¯ ). Their spectroscopic, thermal, and fluorescence properties have also been studied.