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

Abstract

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.

Crystallization of copper(II) sulfate based minerals and MOF from solution: Chemical insights into the supramolecular interactions

“…13 We further extended this mechanistic approach to many other systems including vanadates and molybdates and suggested molecular interpretation for the occurrence of water clusters, polymorphs, pseudopolymorphs, interpenetrated networks, hydration and solvation. [14][15][16][17][18][19] Recently for the first time we employed the retrosynthetic analysis to interpret the packing of several minerals and materials crystallized from the system CuCl 2 -H 2 O-CuO-organic in terms of supramolecular interactions. 20 The retrosynthetic analysis 21 employed in our studies is an integrated approach involving the concepts of Corey's synthon, Desiraju's supramolecular synthon 22 and Wuest's tecton.…”

Hydrothermal syntheses and crystal structures of two new phosphomolybdates based on an organoamine template

“…Among these classical anions, pentamolybdodiphosphate, which was structurally characterized by Strandberg [9] in 1973, has a vital role in polyoxomolybdate-phosphorus. Zubieta and coworkers [10][11][12][13][14][15][16] reported a series of new hybrid compounds based on organophosphonate, Wang and coworkers [17][18][19][20] synthesized new crystals using phosphoric acid and others [21][22][23][24][25][26][27].…”

Structure, Spectroscopic, Magnetic, Fluorescence, and Thermal Studies of Bis(perchlorate)tetrakis(pyrazole)copper(II)

“…Many of these complexes have been studied as a model for enzyme compounds. Other similar Cu(II) organic heterocyclic compounds have been reported [15][16][17][18][19][20][21][22][23] because of their structural interest and their chemical application as catalyst. [24] …”