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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.

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.

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 .

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.

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.