Growth of Copper Pyrazole Complex Templated Phosphomolybdates: Supramolecular Interactions Dictate Nucleation of a Crystal

作者：J. Thomas, Arunachalam Ramanan · 发表于：Crystal Growth & Design · 年份：2008 · DOI：10.1021/cg800344h · 被引用次数：99 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Polyoxometalates: Synthesis and Applications、Supramolecular Self-Assembly in Materials

Five copper pyrazole complex based phosphomolybdates are self assembled at room temperature from an aqueous solution containing sodium molybdate, cupric chloride, and pyrazole acidified with phosphoric acid: one-dimensional (1D) chains in [{Cu (pz )(H 2 O)}{Cu (pz ) 3 (H 2 O)}{Cu (pz ) 4 }{P 2 Mo 5 O 23 }], 1, copper pyrazole complex intercalated two-dimensional (2D) sheets in {Cu (pz ) 2 (H 2 O) 4 }[{Cu (pz ) 2 (H 2 O)} 2 {Cu (pz ) 4 } 2 {HP 2 Mo 5 O 23 } 2 ]·6H 2 O, 2, hexadecameric water clusters incorporated between 1D chains in [{Cu (pz ) 4 } 3 {Cu (pz ) 3 (H 2 O)} 2 {HP 2 Mo 5 O 23 } 2 ]·9H 2 O, 3, a water-mediated interpenetrated three-dimensional (3D) network in [{Cu (pz ) 4 } 2 {H 2 P 2 Mo 5 O 23 }]·H 2 O, 4, and copper pyrazole complex pillared 2D phosphomolybdate sheets in [{Cu (pz ) 2 }P 2 Mo 2 O 12 (H 2 O) 2 ], 5 . Detailed structural characterization of these solids was established by single crystal and powder X-ray diffraction techniques, FTIR, and thermal analysis. This paper proposes intuitive mechanisms to provide molecular insights into the role of in situ copper pyrazole complexes generated in solution in dictating a particular supramolecular assembly which eventually influences the nucleation of a crystal through a concerted condensation process. The role of the complexes as intercalant, pillaring unit, etc. has been demonstrated by these examples.