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A new inorganic-organic hybrid polyoxoboroniobate {H 4 K 2 [Cu( cis -en) 2 (H 2 O)] 9 [Cu( cis -en) 2 ] 6 [Cd 2 ( cis -en) 2 ( trans -en)][LiB 2 Nb 29 O 86 ] 2 ·79H 2 O} ( 1 , en = ethylenediamine), is built from pagoda-shaped {LiB 2 Nb 29 O 86 } clusters, linear {Cd 2 ( cis -en) 2 ( trans -en)} bridging units, and copper-amine complexes. The {LiB 2 Nb 29 O 86 } cluster represents the first example of combining oxoboron clusters with polyoxoniobate clusters (PONbs). It consists of an unusual HPONb fragment {LiNb 18 O 54 }, a fused-ring structural boroniobate cluster {B 2 Nb 5 O 13 }, and a classical Lindqvist {Nb 6 O 19 } fragment. The {Cd 2 ( cis -en) 2 ( trans -en)} and [Cu( cis -en) 2 ] 2+ complexes link the pagoda-shaped {LiB 2 Nb 29 O 86 } clusters into 1D infinite ladder chains. This is the first instance of simultaneous coordination of the cis -en and trans -en ligands with a single metal cation in the inorganic-organic hybrid PONb family. Furthermore, 1 exhibits good proton conductivity.

In this research, indium ions were introduced into polyoxoniobates (PONbs) reaction systems to facilitate the construction of different {SiNb 18 O 54 }-based aggregates, including an {In(en) 2 {SiNb 18 O 54 } 2 } (en = ethylenediamine) dimer, an {[InO 2 ][In 2 (en)O 3 ] 2 {SiNb 18 O 54 } 3 } trimer, and an {[In(en) 2 ][InO 2 ][In 7 (en) 5 O 9 ]{SiNb 18 O 54 } 4 } tetramer. Interestingly, these aggregates were further assembled into three uncommon extended PONb architectures in the presence of [Cu(en) 2 ] 2+ complexes, namely, H 3 [Cu(en) 2 (H 2 O)][Cu(en) 2 ] 6 [Cu(en) 2 ] 2 {[In(en) 2 ][K 2 {SiNb 18 O 54 }(H 2 O) 6 ] 2 }·1.5en·16H 2 O, H 9 {[Cu(en) 2 ] 6 {[Cu(en) 2 ] 3 [Cu(en) 2 (H 2 O)][In(H 2 O) 2 ][In 2 (en)(H 2 O) 2 (OH)] 2 {SiNb 18 O 54 } 3 }·5en·29H 2 O, and H 14 [Cu(en) 2 ] 0.5 [Cu(en) 2 (H 2 O)]{[Cu(en) 2 ] 2 {[Cu(en) 2 ] 3 [Cu(en) 2 (H 2 O)] 5 [K(H 2 O) 2 ][In(H 2 O) 2 ][In(en) 2 ][In 7 (OH) 9 (en) 5 ]{SiNb 18 O 54 } 4 }·7en·39H 2 O. In addition, all of them have good water vapor adsorption capacities and moderate proton transport capabilities. The above results indicate that introducing suitable heteroatoms to induce the aggregation PONb building blocks and further assembling them into new structures is an effective strategy to enrich the PONbs' structural diversity and develop new functional materials.

By variation of the amount of GeO 2 , two organic-inorganic hybrid germanoniobate frameworks with 6-connected pcu and 10-connected bct topologies were constructed from peanut-shaped {α-Ge 12 Nb 38 } and {β-Ge 12 Nb 38 } clusters, respectively. The {α-Ge 12 Nb 38 } and {β-Ge 12 Nb 38 } clusters contain the most Ge centers of germanoniobates reported so far. The compounds exhibit proton conduction properties with a conductivity of 3.04 × 10 -4 S·cm -3 for 1 and 1.62 × 10 -4 S·cm -3 for 2 at 85 °C and 98% RH. The water vapor adsorption capacities for 1 and 2 are 5.86 and 4.40 mmol·g -1 , respectively.

Two new extended polyoxometalate (POM) architectures based on lanthanide-incorporated polyoxoniobate (Ln-incorporated PONb) cages, namely, H 4 [Cu II (en) 2 ] 4 {K 4 (H 2 O) 2 [Cu II (en) 2 ] 5 [Cu II 5 (trz) 2 (en) 4 (OH) 2 ][Dy 2 Cu II 2 (en) 2 (CO 3 ) 3 (H 2 O) 2 (OH) 3 ][Dy(H 2 O) 4 ][DyNb 23 O 68 (H 2 O) 4 ] 2 }·60H 2 O ( 1 , en = ethylenediamine) and H 20 [Cu II (en) 2 ] 4 {[Cu II (en) 2 ] 4 [Dy 2 (C 2 O 4 )(H 2 O) 4 ] 2 [(Nb 32 (OH) 4 (H 2 O) 3 O 89 ] 2 }·54H 2 O ( 2 ), have been successfully synthesized and structurally characterized, demonstrating a feasible strategy to develop functional POM materials. In addition, the proton conductivity and magnetic behaviors of both 1 and 2 were studied.

A stable 3 d -4 f heterometallic cluster, namely, {Dy 4 Ni 5 L 10 (NO 3 ) 4 (CO 3 ) 4 (CH 3 OH) 2 }·CH 3 CN (Dy 4 Ni 5 , HL = 8-hydroxyquinoline), has been solvothermally synthesized and structurally characterized. The compound exhibits an interesting structure in which a tetrahedron based on 4 f ions interpenetrates with a square pyramid based on 3 d ions. Besides, a unique intermolecular interaction was found in Dy 4 Ni 5 , giving rise to its high stability not only when it is in the solid state but also when it dissolves in organic solvents. In addition, the magnetic behavior of solid Dy 4 Ni 5 and the magneto-optical activity of the Dy 4 Ni 5 solution were also studied.

A rare 3D Indium-containing polyoxoniobate framework {H 9 [Cu(en) 2 (H 2 O) 2 ][Cu(en) 2 ] 12 [In(en)] 5 [Nb 23 -O 65 (OH) 3 (H 2 O) 2 ]{Nb 24 O 67 (OH) 2 (H 2 O) 3 ] 2 }·68H 2 O( 1 ), based on the In-containing polyoxoniobate cluster, {[In(en)] 5 [Nb 23 O 65 (OH) 3 (H 2 O) 2 ][Nb 24 O 67 (OH) 2 (H 2 O) 3 ] 2 } 35- ({In 5 Nb 71 }) and [Cu(en) 2 ] 2+ linkers has been successfully synthesized. The nest-like cluster {In 5 Nb 71 } is constructed from one brand-new V-shaped {Nb 23 O 70 }, two triangle-shaped {Nb 24 O 72 } and five [In(en)] 3+ . The [In(en)] fragments link {Nb 24 O 72 } and {Nb 23 O 70 } units into unique {In 5 Nb 71 } n helical pillars. The copper-amine complexes connect the {In 5 Nb 71 } n helical pillars into a three-dimensional (3D) inorganic-organic hybrid In-Cu-containing framework. This material also exhibits good ionic conductivity and vapor adsorption capacity properties.

The assembly of heterometallic cluster substituted polyoxometalates (POMs) remains a great challenge for inorganic synthetic chemistry up to now. Herein, a series of 5p-4f heterometallic cluster substituted POMs were successfully isolated by a facile one-step hydrothermal reaction method, namely H 17 (H 2 en) 3 [Sb III 9 Sb V Ln 3 O 14 (H 2 O) 3 ][(SbW 9 O 33 ) 3 (PW 9 O 34 )]·28H 2 O( 1-Ln , Ln = Ce, Sm, Eu, Gd, Tb, Dy) (en = ethylenediamine). Interestingly, by replacing en with imidazole, another series of 5p-4f heterometallic cluster substituted POMs H 13 (HIm) 4 K 2 Na 4 (H 2 O) 9 [Sb III 9 Sb V Ln 3 O 14 (H 2 O) 3 ][(SbW 9 O 33 ) 3 (PW 9 O 34 )]·26H 2 O ( 2-Ln , Ln = Sm, Eu, Gd, Tb, Dy, Im = imidazole) were obtained. Structural analyses indicate that both 1-Ln and 2-Ln are made up of an unprecedented 5p-4f heterometallic {Sb 10 Ln 3 O 14 (H 2 O) 3 } cluster stabilized simultaneously by mixed trilacunary heteropolyanions including {A-α-PW 9 O 34 } and {B-α-SbW 9 O 33 }. Impedance measurements indicate that both compounds exhibit different proton conduction properties, and the conductivity of 2 can reach up to 1.64 × 10 -2 S cm -1 at 85 °C under 98% relative humidity. Moreover, the fluorescence emission behaviors of both compounds have been studied.

A tetratellurium-substituted heteropolyoxoniobate with the formula K 2 H[Cu(phen)(H 2 O)] 4 [Cu(phen)] 2 [(LiNb 8 Te 4 O 40 )]·34H 2 O ( 1 ; phen = 1,10-phenanthroline) was hydrothermally prepared and structurally characterized. The compound represents the first hexavalent tellurium-substituted Keggin-type polyoxometalate (POM) so far. What is more, the POM cluster in 1 can elaborately self-assemble into a stable supramolecular framework with an ion conduction property through unique intermolecular π-π stacking.

A series of 3D porous lanthanide-substituted polyoxometalate frameworks, Na 2 [Ln 2 (H 2 O) 11 ] 2 [Ln 3 (H 2 O) 3 (α-SiW 11 O 39 ) 2 ] 2 ·69H 2 O ( 1-Ln , Ln = Sm, Eu, Gd, Tb, and Dy), are built from novel hexadecahedral {Ln 6 W 8 O 28 } heterometallic cage-shaped clusters. Intriguingly, every tetrameric {[Ln 3 (H 2 O) 3 (α-SiW 11 O 39 ) 2 ] 2 } 14- cage-cluster is linked with another eight tetrameric cage-clusters by Ln 3+ cations, leading to a novel 3D inorganic porous framework, which exhibits good thermal and chemical stability, excellent water vapor adsorption capacity, and moderate proton conductive properties. Furthermore, the solid state luminescence spectra demonstrate that 1-Sm , 1-Eu , 1-Tb , and 1-Dy display the lanthanide characteristic emission bands. The temperature-dependent magnetic susceptibility indicates that there are antiferromagnetic interactions in 1-Tb and 1-Dy .

Four seven-nuclearity 3d-4f heterometallic cluster {Fe 6 LnO 28 } substituted polyoxometalates (HPz) 11 K 4 Fe 6 Ln(μ 3 -O) 2 (B-α-GeW 9 O 34 ) 2 (GeW 6 O 26 )· xH 2 O (1-Ln, Pz = piperazine, Ln = Tb, Dy, Ho, Er for x = 27, 25, 25, 24, respectively) have been hydrothermally prepared and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectrometry, thermogravimetric analyses, elemental analyses, and electrospray ionization mass spectrometry. Single-crystal X-ray diffraction analyses revealed that 1-Ln contain an unprecedented banana-shaped polyanion constructed from an iron-lanthanide heterometallic {Fe 6 LnO 28 } cluster, two trilacunary {B-α-GeW 9 O 34 } units, and one hexalacunary {GeW 6 O 26 } fragment. The magnetic susceptibility surveying proved the presence of antiferromagnetic coupling in 1-Ln.

The two novel cluster organic frameworks based on heterometallic supertetrahedral cluster secondary building units (SBUs) [Cd 4 Cu 6 (L) 4 (Ac) 7 (H 2 O) 4 ](Ac)·7H 2 O (1) and [Mn 4 Cu 6 (L) 4 (Ac) 4.5 (H 2 O) 9 ]CuCN(Ac) 3.5 ·H 2 O (2), where H 3 L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol and Ac = CH 3 COO - , have been prepared under solvothermal conditions. 1 and 2 are the first cases of cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral cluster SBUs. Furthermore, 1 and 2 show an integration of magnetic properties and adsorption properties from both the heterometallic cluster secondary building units and the framework in a porous material.

Two novel cluster-organic frameworks based on the 12-nuclearity manganese-cluster secondary building unit (SBU), [Mn III 4 Mn II 8 (L) 4 (Ac) 8 (MeO) 2 (μ 5 -O) 2 (H 2 O) 4 ](Ac) 2 ·16H 2 O (1) and [Mn III 4 Mn II 8 (L) 4 (Ac) 8 (MeO) 2 (μ 5 -O) 2 (H 2 O) 4 ](Ac) 2 ·12H 2 O (2), where Ac = CH 3 COO - and MeO = CH 3 O, have been constructed from solvothermal reactions of the 3-nuclearity manganese cluster [Mn 3 (μ 3 -O)(Ac) 6 (py) 3 ](ClO 4 ) (Mn 3 , where py = pyridine) with a tripodal alcohol ligand containing a 4-pyridyl group. 1 and 2 represent the first examples of metal-organic frameworks containing 12-nuclearity manganese-cluster SBUs. In addition, 1 exhibits an integration of the porosity and magnetic properties from both the framework and cluster in a porous material.

A step-by-step synthetic strategy, setting up a bridge between the polyoxometalate (POM) and metal halide cluster (MHC) systems, is demonstrated to construct an unprecedented composite hybrid cluster built up from one high-nuclearity cationic MHC [Cu8I6](2+) and eight Anderson-type anionic POMs [HCrMo6O18(OH)6](2-) cross-linked by a tripodal alcohol derivative.

A bifunctional metalloligand with metal-C (Ge-C) bonds, bis(carboxyethylgermanium) sesquioxide (H(2)E(2)Ge(2)O(3), where E = -CH(2)CH(2)COO(-)), has been used to make metal-organometallic frameworks (MOMFs) Cd(1.5)(E(3)Ge(3)O(5)) (1) and Pb(E(2)Ge(2)O(3)) (2). In the structures, the inorganic Ge(2)O(3) cores of the metalloligands polymerize to form two kinds of infinite Ge-O chains, and the organic carboxyls induce the Cd and Pb ions to produce Cd-O and Pb-O chains. Further, the Ge-O chains link the Cd-O/Pb-O chains via -CH(2)CH(2)- groups to result in two novel MOMFs, showing high thermostability and blue-violet emission.

Reaction of CuCl(2) x 2 H(2)O and trivacant Keggin polyoxoanion Na(9)[A-alpha-PW(9)O(34)] x 7 H(2)O in the presence of ethylene-diamine/1,2-diaminopropane (en/enMe) under hydrothermal conditions led to five novel inorganic-organic hybrid polyoxotungstates (POTs):[Cu(en)(2)](2)[Cu(en)(2)(H(2)O)](2)[Cu(H(2)O)(2)][Cu(4)(H(2)O)(2)(B-alpha-PW(9)O(34))(2)] x 2 H(2)O(1), [Cu(6)(mu(3)-OH)(3)(en)(3)(H(2)O)(5)(B-alpha-PW(9)O(34))] x 6 H(2)O (2), Na(6){[Cu(6)(mu(3)-OH)(3)(en)(3)(H(2)O)(2)(B-alpha-PW(9)O(34))](2)[Cu(4)(H(2)O)(2)(B-alpha-PW(9)O(34))(2)]} x 2 H(2)en x 8 H(2)O (3), [Cu(6)(mu(3)-OH)(3)(en)(3)(H(2)O)(3)(B-alpha-PW(9)O(34))] x 4 H(2)O (4), [Cu(II)(6)Cu(I)(4)(mu(6)-O)(OH)(18)][Cu(6)(mu(3)-OH)(3)(enMe)(3)(H(2)O)(3)(B-alpha-PW(9)O(34))](4) x 4 H(3)O x 2 H(2)O (5). 1 is a new 1D chain constructed from alternate tetra-Cu(II) sandwiched units [Cu(II)(4)(H(2)O)(2)(B-alpha-PW(9)O(34))(2)](10-) and dinuclear [Cu(II)(2)(H(2)O)(6)](4+) units. 2-5 are a series of novel transition-metal substituted polyoxometalates (TMSPs) comprising hexa-Cu(II) substituted {Cu(6)PW(9)} units (Cu(6) = Cu(6)(mu(3)-OH)(3), PW(9) = B-alpha-PW(9)O(34), Scheme 1). 2 is an unusual monomer. 3 is an unprecedented tetramer built by two types of TMSP units, [Cu(6)PW(9)(en)(3)(H(2)O)(2)] and [Cu(II)(4)(H(2)O)(2)(PW(9))(2)](10-). 4 is a novel chain assembled from [Cu(6)PW(9)(en)(3)(H(2)O)(3)] units by double-bridging mode. Most interestingly, 5 is a open framework made by [Cu(6)PW(9)(enMe)(3)(H(2)O)(3)] units, in which the novel decacopper oxygen clusters, [Cu(I)(4)Cu(II)(6)(mu(6)-O)(OH)(18)](4-) formed in situ, are encapsulated into the channels, and 5 represents the first decametallic-cluster-containing open framework built by TMSP units. 2-5 all contain the hexa-Cu(II) substituted POT unit {Cu(6)PW(9)L(3)(H(2)O)(n)} (L = en/enMe, n < 6) made by {Cu(6)L(3)(H(2)O)(n)} core and trivacant Keggin PW(9) fragments. Moreover, 3-5 can be viewed as combining derivatives of 2 through substituting water ligands on hexa-Cu(II) {Cu(6)L(3)(H(2)O)(n)} units by terminal oxygen atoms of PW(9) units. Importantly, the Cu(II)-polyhedra Jahn-Tell/pseudo-Jahn-Teller distortion plays a crucial role in the formation of 1-5. The magnetic behaviors of 2-5 show antiferromagnetic interactions between the Cu(II) ions in the hexa-Cu(II) cluster.

Three novel 3D pillared-layer heterometallic lanthanide-transition-metal (hetero-Ln-TM) compounds, namely, Ln2Cu7I6(ina)7(H2O)6.H2O [ina=isonicotinic acid; Ln=Ce (1), Sm (2)] and Er4(OH)4Cu5I4(ina)6(na)(2,5-pdc).0.3H2O (3; na=nicotinic acid, 2,5-pdc=2,5-pyridinedicarboxylic acid), have been obtained by incorporating different metal clusters as building blocks under hydrothermal conditions. Compounds 1 and 2 are isostructural and consist of two distinct building units of dimeric [Ln2(ina)6] cores and inorganic 2D [Cu8I7]nn+ layers based on the [Cu3I3] and [Cu4I3]+ clusters. Compound 3 is constructed from decanuclear [Cu10I8]2+ clusters and inorganic 1D [Er4(OH)4]n8n+ cluster chain-based layers, which represent the first example of a 3D hetero-Ln-TM constructed by the combination of two distinct types of metal cluster units of a 1D [Er4(OH)4]n8n+ cluster polymer and a transition-metal cluster. It is interesting that decarboxylation occurred in the ortho position and 2,5-pdc2- was partially transformed into na- under hydrothermal conditions. Compounds 1-3 represent good examples of using different metal cluster units to construct fascinating 3D hetero-Ln-TM frameworks.

A novel tetrameric cluster, (enH2)3.5H15[{FeIIFeIII12(mu3-OH)12(mu4-PO4)4}(B-alpha-PW9O34)4].83H2O (1; en = ethylenediamine), has been hydrothermally synthesized and characterized by IR, optical diffuse reflectance, thermogravimetric analysis, and single-crystal X-ray diffraction. The skeleton of 1 is composed of four tri-FeIII-substituted [FeIII3(mu3-OH)3(B-alpha-PW9O34)]3- Keggin moieties fused together through a FeII2O2 unit and four mu4-PO4 bridges, resulting in a unique tetramer with C2 symmetry. Magnetic measurements indicate that 1 reveals the antiferromagnetic interactions between FeII and FeIII centers.

A new series of heterometallic lanthanide(III)-copper(I) coordination polymers Ln2(bdc)2(ina)2(H2O)2Cu x X (Hina = isonicotinic acid; H2bdc = 1,2-benzenedicarboxylic acid; Ln = Eu (1), Sm (2), Nd (3), X = ClO4-; Ln = Nd (4), X = Cl-) have been hydrothermally synthesized in the presence/absence of HClO4. Both compounds are isostructural and contained two distinct units of 2D Ln-bdc layers and linear [Cu(ina)2]-. The linear [Cu(ina)2]- complexes act as pillars and further link the Ln-bdc layers resulting in four heterometallic metal-organic frameworks, which represent the first pillared-layer 3d-4f framework with two distinct types of channels along the b and c axes. The compounds can be specified by the Schläfli symbol (47.63)(47.68) as a novel 3D (5,6)-connected net. Furthermore, the IR, TGA, PXRD, and UV-vis spectral and luminescent properties of 1-4 were also studied.

Hydrothermal reactions of lanthanide(III) oxide and copper halide with isonicotinic acid (Hina) and pyridine-2,3-dicarboxylic acid (H2pdc) or 1,2-benzenedicarboxylic acid (H2bdc) lead to three novel lanthanide(III)-copper(I) heterometallic compounds, namely, [Ce2(ina)5(na)2(H2O)2][Cu5Br4] (1, na=nicotinic acid), [Er4(ina)8(bdc)2(OH)(H2O)5][Cu8I7] (2), and [Ce3(ina)8(bdc)(H2O)4][Cu7Br6] (3). Compound 1 is constructed from two distinct units of the Ln-organic double chains and inorganic [Cu5Br4]nn+ chains. Compound 2 consists of 2D Ln-organic layers and 1D [Cu8I7]nn+ cluster chains. Compound 3 can be viewed as a 1D [Cu6Br6]n chainlike motif inserted into the channels of a 3D Ln-Cu-organic motif. Compounds 1-3 exhibit three different 1D inorganic copper(I)-halide chains interconnected with metal-organic 1D chains, 2D layers, and 3D nets resulting in three mixed-motif non-interpenetrating heterometallic Cu-halide-lanthanide (Ln)-organic frameworks, which represent good examples and a facile method to construct such mixed-motif heterometallic compounds. Furthermore, the IR, TGA, and UV-vis spectra of 1-3 were also studied.

A novel polyoxovanadate (POV), [Zn(2,2'-bpy)3]4[(ppz){{Zn(tepa)}2ZnAs8V13O41(H2O)}2][As8V14O42(0.5H2O)]2.4H2O (1, 2,2'-bpy = 2,2'-bipyridine, ppz = piperazine, tepa = tetraethylenepentamine), has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectra, thermogravimetric analysis, magnetic measurement, and single-crystal X-ray diffraction analysis. Crystal data for 1: orthorhombic, Aba2, a = 28.3414(14) A, b = 27.9995(16) A, c = 41.5819(16) A, V = 32997(3) A3, Z = 4, rho = 2.264 mg.cm-3. X-ray structure analysis shows that the structure of 1 consists of one unique zinc-substituted POV dimer and two POV monomers. Interestingly, the formation of the zinc-substituted POV dimer involves two new in situ ligand reactions under hydrothermal conditions, the intermolecular and intramolecular deamination coupling reactions of dien. Magnetization measurement revealed the presence of antiferromagnetic interaction between V(IV) ions in 1.

A novel sandwich-type polyoxometalate incorporating a unique hybrid hexanuclear copper cluster, [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}.4H2O (1, enMe=1,2-diaminopropane), has been hydrothermally synthesized and structurally characterized by the elemental analyses, IR spectroscopy, TG analysis, magnetic properties, and single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, P; a=12.5105(2), b=14.3710(2), c=17.2687(2) A; alpha=98.834(1), beta=110.744(1), gamma=104.711(1) degrees; V=2704.57(7) A3; rho=3.646 g/cm3; Z=1. X-ray crystallographic study shows that the molecular structure of 1 contains 10 copper ions: Six of them form an unprecedented inorganic-organic hybrid Cu6 cluster via edge-sharing combination of two CuO6 octahedra, two CuO5, and two CuO3N2 square pyramids and are encapsulated between two {B-a-SiW9O34} units. Two of them form two [Cu(enMe)2(H2O)]2+ complexes and further attach to the two {B-a-SiW9O34} units via two Cu-O=W bridges, acting as a decorated role. The remaining two form isolated [Cu(enMe)2]2+ complexes playing roles of charge-compensation and space-fillers. Magnetization measurement reveals that the hexanuclear copper cluster exhibits overall ferromagnetic interactions.

Two copper-complex-substituted tungstogermanates [Cu5(2,2'-bpy)6(H2O)][GeW8O31].9H2O, 1, and {[Cu5(2,2'-bpy)5(H2O)][GeW9O34]}2.7H2O, 2 (2,2'-bpy = 2,2'-bipyridyl), have been hydrothermally synthesized and structurally characterized. X-ray structural analyses show that 1 is a rare tetralacunary Keggin anion of [B-beta-GeW8O31]10- substituted by copper complexes, while dimer 2 consists of two trilacunary [B-alpha-GeW9O34]10- Keggin units bridged by copper complexes. Magnetic measurement for 2 shows the presence of antiferromagnetic interactions within the dinuclear Cu2+ cations.

Two new niobium and zinconiobium fluorophosphates, NbOF(PO4)2(C2H10N2)2 (1) and Zn3(NbOF)(PO4)4-(C2H10N2)2 (2), have been prepared under hydrothermal conditions using ethylenediamine as a template. The structures were determined by single crystal diffraction to be triclinic, space group P1 (No. 2), a = 8.1075 (6) A, b = 9.8961 (7) A, c = 10.1420(8) A, alpha = 111.655(1) degrees, beta = 111.51(1) degrees, gamma = 93.206(1) degrees, V = 686.19(9) A3, and Z = 2 for 1 and orthorhombic, space group Fddd (No. 70), a = 9.1928(2) A, b = 14.2090(10) A, c = 32.2971 (6) A, V = 4218.66(12) A3, and Z = 8 for 2, respectively. Compound 1 is an infinite linear chain consisting of corner-sharing [Nb2P2] 4-MRs bridged at the Nb centers with organic amines situated between chains, and compound 2, containing the chains similar to that in 1, forms a zeotype framework with organic amines situated in the gismondine-type [4684] cavities. The topology of 2 was previously unknown with vertex symbol 4 x 4 x 4 x 4 x 8 x 8 (vertex 1), 4 x 4 x 4 x 82 x 8 x 8 (vertex 2), 4 x 4 x 8 x 8 x 82 x 82 (vertex 3), and 4 x 4 x 4 x 82 x 8 x 8 (vertex 4). The topological relationships between the 4-connected network of 2 and several reported (3,4)-connected networks were discussed.

Two new cadmium-substituted polyoxovanadates of [Cd(dien)2]2[(dien)CdAs8V13O41(H2O)].4H2O and [Cd(en)2]2[(en)2Cd2As8V12O40] (2), where dien is diethylenetriamine and en is ethylenediamine, have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, EPR spectra, XRD spectra, TG analyses, magnetic properties, and X-ray crystallography. Single-crystal X-ray diffraction analyses reveal that compounds 1 and 2 possess a discrete and 1D structure, respectively. The former contains an inorganic-organic hybrid monocadmium-substituted polyoxovanadate cluster unit that is derived from the well-known {As8V14O42} cluster, whereas the latter is composed of an inorganic-organic hybrid bicadmium-substituted polyoxovanadate cluster unit that is derived from the well-known {As8V12O40} cluster.

The first organically templated 3D borogermanate with a novel zeolite-type topology, (C4N3H15)[(BO2)2(GeO2)4] FJ-17, has been solvothermally synthesized and characterized by IR spectroscopy, powder X-ray diffraction (PXRD), TGA, and single-crystal X-ray diffraction. The compound crystallized in the monoclinic space group P2(1)/c with a = 6.967(1) A, b = 10.500(1) A, c = 20.501(1) A, beta = 90.500(3) degrees , V = 1499.68(8) A3, and Z = 4. The framework topology of this compound is the previously unknown topology with the vertex symbols 3.4.3.9.3.8(2) (vertex 1), 3.8.3.4.6(2).9(2) (vertex 2), 3.8(2).4.6(2).6(2).8 (vertex 3), 4.8.4.8.8(3).12 (vertex 4), 4.8.4.8.8(2).12 (vertex 5), and 3.8.4.6(2).6.8(2) (vertex 6). The structure is constructed from Ge8O24 and B2O7 clusters. The Ge8O24 cluster contains eight GeO4 tetrahedra that share vertices; the B2O7 unit is composed of two BO4 tetrahedra sharing a vertex. The cyclic Ge8O24 clusters connect to each other through vertices to form a 2D layer with 8,12-nets. The adjacent layers are further linked by the dimeric B2O7 cluster units, resulting in a 3D framework with 12- and 8-ring channels along the a and b axes, respectively. In addition, there is a unique B2GeO9 3-ring in the structure.

The novel polyoxometalate ([As(8)V(13)NiClO(41)][Ni(en)(2)(H(2)O)][Ni(en)(2)])([Ni(en)(2)(H(2)O)(2)](0.5)).4H(2)O (1), which is the first example of a chainlike inorganic-organic hybrid polymer based on dimeric polyoxoanions linked by nickel complex fragments, has been synthesized in the system of As(2)O(3)-V(2)O(5)-H(2)C(2)O(4)-en-NiCl(2).6H(2)O-H(2)O under hydrothermal conditions and characterized by IR, TGA, elemental analysis, single crystal X-ray diffraction, XPS, and magnetic susceptibility studies, respectively. This compound crystallized in the triclinic space group P with a = 13.358(3) angstroms, b = 14.198(3) angstroms, c = 19.723(4) angstroms, alpha = 83.88(3) degrees, beta = 86.04(3) degrees, gamma = 64.66(3) degrees, V = 3360.2(2) angstroms(3), and Z = 2. Interestingly, the dimeric polyoxoanion contains two ([Ni(en)(2)(H(2)O)][As(8)V(13)NiClO(41)]) cluster units linked by Ni-O-As bonds and is a Ni-substituted [As(8)V(13)NiClO(41)] cluster supported by [Ni(en)(2)(H(2)O)] coordination fragment. The chainlike structure consists of ([Ni(en)(2)(H(2)O)][As(8)V(13)NiClO(41)])(2) dimeric polyoxoanions and [Ni(en)(2)] groups which are linked together through vertexes forming a unique one-dimensional polymer. The study of the magnetic susceptibility of 1 demonstrates the presence of antiferromagnetic interaction in 1.

The first noncentrosymmetric potassium templated borogermanate, K(2)[Ge(B(4)O(9))].2H(2)O, has been solvothermally synthesized and characterized by IR, SEM, powder X-ray diffraction (PXRD), TGA, energy dispersive spectroscopy (EDS), single crystal X-ray diffraction, and second harmonic generation (SHG) activity, respectively. This compound crystallized in the monoclinic space group Cc with a = 6.793(1) A, b = 12.0699(3) A, c = 11.895(3) A, beta = 91.156(4) degrees, V = 975.1(4) A(3), and Z = 4. Interestingly, the structure possesses a unique 3D alternating linkage mode of B(4)O(9) clusters and GeO(4) units and contains two pairs of interweaving double helical channels with a 10-membered ring. In one, the right- and left-handed helices couple each other, and in the other, the left- and right-handed helices couple together. The compound exhibits distinct nonlinear optical (NLO) properties because it lacks a symmetric center. Furthermore, the framework of the title compound not only displays high thermal stability but also can be recoverable to a large degree during a dehydration-hydration cycle.

The first chainlike germanate, [Ge(7)O(13)(OH)(2)F(3)](3)(-).Cl(-).2[Ni(dien)(2)](2+), has been solvothermally synthesized by using Ni(dien)(2)(2+) cations as the template and characterized by IR, SEM, TGA, powder X-ray diffraction (PXRD), energy-dispersive X-ray analysis (EDXA), elemental analysis, and single-crystal X-ray diffraction, respectively. This compound crystallized in the monoclinic space group P2/nwith a = 8.8904(2) A, b = 17.4374(3) A, c = 13.2110(3) A, beta = 101.352(1) degrees, V = 2007.97(7) A(3), and Z = 2. Interestingly, the structure contains two types of chiral mer-[Ni(dien)(2)](2+) cations and two types of chiral chains, one left-handed and the other right-handed, which lead to a racemic compound. The orderly separation of achiral s-fac-[Ni(dien)(2)](2+) and chiral mer-[Ni(dien)(2)](2+) isomers was found in the structure. The structure is stabilized by N-H.O(F, Cl) hydrogen bonds.