Polyoxometalates represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form structures that can bridge several length scales. The new building block principles that have been discovered are beginning to allow the design of complex clusters with desired properties and structures and several structural types and novel physical properties are examined. In this critical review the synthetic and design approaches to the many polyoxometalate cluster types are presented encompassing all the sub-types of polyoxometalates including, isopolyoxometalates, heteropolyoxometalates, and reduced molybdenum blue systems. As well as the fundamental structure and bonding aspects, the final section is devoted to discussing these clusters in the context of contemporary and emerging interdisciplinary interests from areas as diverse as anti-viral agents, biological ion transport models, and materials science.

Polyoxometalate clusters, nanostructures and materials: From self assembly to designer materials and devices

Deconstructing the Crystal Structures of Metal Organic Frameworks and Related Materials into Their Underlying Nets Michael O’Keeffe* and Omar M. Yaghi* Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287, United States Center for Reticular Chemistry, Center for Global Mentoring, Department of Chemistry and Biochemistry, University of California Los Angeles, 607 Charles E. Young Dr. East, Los Angeles, California 90095, United States Graduate School of EEWS, Korea Advanced Institute of Science and Technology, Daejeon, Korea

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Deconstructing the crystal structures of metal-organic frameworks and related materials into their underlying nets.

Note: Times Cited: 875 Reference EPFL-ARTICLE-206025doi:10.1021/cr0501846View record in Web of Science URL: ://WOS:000249839900009 Record created on 2015-03-03, modified on 2017-05-12

Complex Hydrides for Hydrogen Storage

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

2.1.2. Low Topology/Framework Density 1003 2.1.3. Side Group Directed Superstructures 1003 2.2. Synthesis Considerations 1003 2.3. Special Properties 1004 3. Metal Imidazolate Frameworks 1004 3.1. Chains and Rings 1004 3.2. Zeolitic and Zeolite-like Frameworks 1006 3.2.1. SOD-Type Zinc(II) 2-Methylimidazolate 1007 3.3. Nonporous 4-Connected Networks 1010 3.4. Polyimidazolates 1011 4. Metal Pyrazolate Frameworks 1011 4.1. Clusters and Chains 1011 4.2. 3D Networks Based on Polypyrazolates 1012 5. Metal 1,2,4-Triazolate Frameworks 1014 5.1. Simple 3-Connected Networks 1015 5.2. Quasi-Imidazolates 1018 5.3. With Coordinative Substituents 1019 5.4. With Secondary Counterions and/or Ligands 1021 6. Metal 1,2,3-Triazolate Frameworks 1023 7. Metal Tetrazolate Frameworks 1025 7.1. Univalent Coinage-Metal Tetrazolate Frameworks 1025

Metal Azolate Frameworks: From Crystal Engineering to Functional Materials

Hydrothermal reaction of Cu(MeCO2)2, (4-pyridylthio)acetic acid, and NH4SCN resulted in a metal-organic framework [Cu3(4-pyridinethiolate)2(CN)] which has twelve-connected face-centered cubic topology with Cu6S4 clusters as nodes.

A twelve-connected Cu6S4 cluster-based coordination polymer.

Morphological properties of AlN piezoelectric thin films deposited by DC reactive magnetron sputtering

Two salts and seven copper(I/II) and silver(I) coordination polymers containing tetrazolyl ligands have been hydro(solvo)thermal synthesized by metal salts, NaN3 and various nitriles generated via [2 + 3] cycloaddition reactions of organonitriles and sodium azide. The study also shows that in some cases the azide can play a dual role in the in situ syntheses of metal tetrazole complexes, namely, starting material for tetrazole ligand and co-ligand in the tetrazole-based coordination complexes. Compounds 1 and 2 are simple salts of ammonium and sodium 5-methyltetrazolate. Compound 3 has a 3-D framework with intersecting channel and unprecedented (49.66) topology constructed from mixed-valent Cu8 clusters. Compounds 4 and 5 are isomorphous, and have 3-D organic–inorganic frameworks constructed by [M2(mtta)]+ (Hmtta = 5-methyltetrazole) ribbon and [M2(N3)]+ (M = Cu, Ag) layer two types of structural motifs, which contains an µ4-1,1,1,3 azide. Compound 6 is a 3-D four-connected chiral complex with (42.84)Cu(42.82.102)tta topology. The structure of 7 consists of 2-D three-connected layers that are linked by ligand-unsupported Ag(I)⋯Ag(I) interactions to form a 3-D supramolecular array. Compound 8 shows a 3-D chiral framework containing tetrahedrally and linearly coordinated Ag(I) ions and µ3- and µ4-two types of 5-propyltetrazolate. Compound 9 has a 2-D layered structure formed by linkage of [Ag(tetrazolyl)] ribbons via C–C and N–Ag bonds. Magnetic measurement confirmed that there are two Cu(II) ions and six Cu(I) ions per Cu8 unit consistent with a mixed-valent Cu(I,II) complex.

Syntheses and structures of metal tetrazole coordination polymers.

The structure and energy of aluminum nitride cages (AlN)n (n = 2−41) have been investigated theoretically. The most stable cages have been constructed on the basis of a simple design principle, and the predicated stability has been validated at the B3LYP/LANL2DZp//HF/LANL2DZ level of theory. Among these, the Th symmetrical (AlN)12 cluster has been computed to be the most stable cage on the basis of the calculated disproportionation energy and binding energy per AlN unit.

Hai-Shun Wu

Papers

A twelve-connected Cu6S4 cluster-based coordination polymer.

Morphological properties of AlN piezoelectric thin films deposited by DC reactive magnetron sputtering

Syntheses and structures of metal tetrazole coordination polymers.

Geometric and Energetic Aspects of Aluminum Nitride Cages

What is the most stable B24N24 fullerene