Two novel organic-inorganic hybrids, Na[PMo(V)8Mo(VI)4O38(OH)2Zn4][pyim]2·1.5H2O [ε(pyim)2] (pyim = 2-(2-pyridyl)-imidazole) and [PMo(V)8Mo(VI)4O37(OH)3Zn4]2[pyim]6·4H2O [ε2(pyim)6], based on ε-Zn Keggin units {ε-PMo(V)8Mo(VI)4O(40-x)(OH)(x)Zn4}, have been successfully synthesized under hydrothermal conditions by controlling the pH values. Structural analysis indicates that the framework of ε(pyim)2 is a 1D chain constructed by monomeric ε-Zn units modified by pyim ligands, while ε2(pyim)6 is an isolated structural compound with dimeric ε-Zn units modified by pyim ligands. This is the first isolated structure of the ε-Keggin POMs system. The luminescent and electrochemical properties of ε(pyim)2 and ε2(pyim)6 were investigated. ε2(pyim)6 also shows high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester (MAP).

A new vanadium sulfate, [H2N(CH3)2](19/3)(en)[V5O5(μ3-O)4(SO4)4](SO4)(2/3)[HN(CH3)2](2/3) 1, constructed from novel umbrella-like [V(V)(μ3-O)4V(IV)4O5(SO4)4(en)](5-) anions was synthesized and structurally characterized using single-crystal X-ray analysis. The magnetic and optical studies of 1 indicate that the title compound exhibits significant ZFS (zero field splitting), interesting ferrimagnetic interactions and strong two photon absorption.

Four two-dimensional fully reduced polyoxovanadates, namely, [Cd(DAP)2]4[HV(III)3V(IV)18P6O60(DAP)3(HOCH2CH2OH)]·10H2O (1), [Cd(DAP)2]4[HV(III)3V(IV)18P6O60(DAP)3(CH3OH)]·11H2O (2), [Cd(DAP)2]4[HV(III)3V(IV)18P6O60(DAP)3(CH3CH2OH)]·4H2O (3) and Co(III)(DAP)3[Co(II)(DAP)2]3[V(III)3V(IV)18P6O60(DAP)3(HOCH2CH2OH)]·14H2O (4) were synthesized by virtue of the reducing power of alkylamine in hydrothermal conditions. Single-crystal X-ray structural analysis, magnetic measurement, IR spectroscopy, elemental analysis, and thermogravimetric measurements were performed to analyze the structures and properties of these four compounds. Structural analysis indicates that the four compounds contain the same huge low-valent vanadium oxide anion cages [V(III)3V(IV)18P6O60(DAP)3](9-), and the cages can catch different guest molecules. Four cages are linked by Co or Cd atoms to form a four-membered ring, while adjacent four-membered rings are connected to each other by sharing edges to make an inorganic-organic hybrid layer. The magnetic susceptibility measurements of four compounds indicate ferrimagnetic interactions between vanadium ions.

Two compounds with L-Chiral helical chains have been solvothermal synthesized: Sm(HCO2)(SO4)(H2O) (1) and KSm (H2O) (SO4)(2) (2). Complex 1 is synthesized without any chiral auxiliary, while complex 2 is the opposite. However, in 2, chiral auxiliaries do not exsit in the inorganic framework but work as the inducer in the formation of the complex. Single-crystal X-ray diffraction (XRD) demonstrates that complex 1 crystallizes in space group P4(1) and complex 2 crystallizes in space group P3(1). Complex 1 is constructed of two types of L-[Sm-O](n) chains, every two different kinds of adjacent helical chains are connected by sharing Sm (TEE) ions to form Intertwined left-handed double helices. Compound 2 is constructed of two L-chiral helical chains: [Sm-O-S1-O](n) and [Sm-O-S2-O](n), the two adjacent helical chains are connected by sharing Sm (III) ions to form double helices chains, every two adjacent double helices chains are connected through K+ linkages to form Intertwined left-handed double helices. The second-harmonic-generation efficiencies and fluorescence of 1 and 2 were studied. CCDC: 977312, 1; 977313, 2.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Compounds 1 and 2 are the first two isolated structures in the family of 2D layered high-nuclear wheel-shaped {Mo/TM/P} clusters. Both compounds show good NLO activities, which are rare in compounds containing POM anions.

Two novel organic-inorganic hybrids, Na[PMo(V)8Mo(VI)4O38(OH)2Zn4][pyim]2·1.5H2O [ε(pyim)2] (pyim = 2-(2-pyridyl)-imidazole) and [PMo(V)8Mo(VI)4O37(OH)3Zn4]2[pyim]6·4H2O [ε2(pyim)6], based on ε-Zn Keggin units {ε-PMo(V)8Mo(VI)4O(40-x)(OH)(x)Zn4}, have been successfully synthesized under hydrothermal conditions by controlling the pH values. Structural analysis indicates that the framework of ε(pyim)2 is a 1D chain constructed by monomeric ε-Zn units modified by pyim ligands, while ε2(pyim)6 is an isolated structural compound with dimeric ε-Zn units modified by pyim ligands. This is the first isolated structure of the ε-Keggin POMs system. The luminescent and electrochemical properties of ε(pyim)2 and ε2(pyim)6 were investigated. ε2(pyim)6 also shows high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester (MAP).

Invited for the cover of this issue is the group of Hua Mei and Yan Xu at Nanjing Tech University, China. The image depicts star-like {Tb26 } clusters, which are simplified as blue balls, and Ag atoms, which are distributed in the MOF structure uniformly to give a lanthanide-MOF structure with good optical properties. Read the full text of the article at 10.1002/chem.201405178.

Two new layered hybrid organic-inorganic compounds [Zn(pyim)]2V4O12 () (pyim = 2-(2-pyridyl)imidazole) and [Cu(bim)2]2V4O12(H2O)·CH3CH2OH () (bim = bis(1-imidazolyl)methane) based on polyoxovanadates (POVs) and organic ligands decorated transition metal units have been synthesized by hydrothermal and solvothermal methods respectively. Single crystal XRD, fluorescence spectrum, magnetic measurement, IR spectra, powder XRD and thermogravimetric (TG) measurements were performed to analyze the structures and properties of and . The structural analysis reveals that compound features a two-dimensional {[Zn(pyim)]2V4O12}n layered structure, constructed by sine wave-like {V4O12}n(4n-) chains, Zn(2+) ions and pyim ligands. In the layered structure of , {V4O12}(4-) circles are connected by Cu(2+) ions to form {Cu(V4O12)}n(2n-) chains, which are further linked by {Cu(bim)4}(2+) subunits to generate a hybrid layer of . The magnetic susceptibility measurement indicates strong antiferromagnetic interactions between Cu(2+) ions in .

A dimeric Keggin polyoxometalate, [Cu(bpy)(μ2-OH)]4[(H2O)(bpy)2HPW11Cu2O39]2·2CH3CH2OH·10H2O (1), constructed from two dicopper(II)-substituted monovacant Keggin polyoxoanions bridged by a Cu4 cluster, has been hydrothermally synthesized. Magnetic analysis indicates predominantly an antiferromagnetic interaction between copper(II) centers. Compound 1 also shows very high catalytic activity for the esterification of phosphoric acid with equimolar lauryl alcohol to monoalkyl phosphate ester.

The first organic amine templated vanadyl pyrophosphate, [H2N(CH3)2]2VO(P2O7) (1), has been synthesized at a relatively mild temperature (180°C) under solvothermal conditions without any pyrophosphates. The structural analysis reveals that compound 1 is constructed by two types of helical chains and protonated dimethylamine cations. Two types of helical chains in 1 are connected through OVO linkages to make a double wave-like [VOP2O7]n chain. Magnetic susceptibility measurement of compound 1 indicates antiferromagnetic interactions between V4+ ions, while the observed SHG efficiency is 0.4 times of urea for 1.

Employing solvothermal method, two new lanthanide sulfates [Tb-2(SO4)(5)][(CH3)(2)NH2](4)(1) and [Y-2(SO4)(5)][(CH3)(2)NH2](4)(2) with two-dimensional layered structures have been synthesized and characterized by single-crystal XRD, ICP, IR and TGA. Both of the two compounds crystallize in the triclinic space group p (1) over bar. Crystal data for 1, a=0.988 7(3) nm, b=1.106 1(3) nm, c=1.535 4(4) nm, alpha=70.45(4)degrees, beta=75.12(3)degrees, gamma=67.11(3)degrees, Z=2. For 2, a= 0.9816(5) nm, b=1.100 1(5) nm, c=1.528 6(8) nm, alpha=70.44(6)degrees, beta=75.45(6)degrees, gamma=67.48(6)degrees, Z=2. Crystal structure analysis reveals that both of the inorganic frameworks of compound 1 and 2 have layered two-dimensional architectures which are formed by two types of double stranded chains and 12-membered rings (12MRs). The solid state luminescent properties of compounds 1 were investigated and it displays a typical luminescent property of Tb3+ with excitation wavelength at 369 nm. CCDC: 941147,1; 941148 2.