Early lanthanoid substituted organic-inorganic hybrids of silico- and germano-tungstates: Syntheses, crystal structures and solid-state properties

Gupta, Rakesh ; Parbhakar, Swati ; Khan, Imran ; Behera, Jogendra Nath; Hussain, Firasat

Abstract

Organic-inorganic hybrid of 3d-4f heterometallic derivatives of lacunary Keggin type silico- and germano-tungstates: [{Cu2(1,10-phen)2(µ-CH3COO)2}Ln(α-XW11O39)2]11‒/10‒ {Ln = LaIII, CeIII and CeIV, X = SiIV; LaIII, CeIII, CeIV, X = GeIV; 1,10-phen = 1,10-Phenanthroline} have been synthesized by conventional aqueous solution method under mild reaction conditions. Solid crystalline materials isolated from the solution as an alkali salts (Na+/K+) are characterized by single crystal X-ray diffraction, FT-IR spectroscopy, powder-XRD, ICP-AES, liquid UV/vis and thermogravimetric analysis. FT-IR spectra and PXRD suggest that these compounds are isomorphous. Further, single crystal XRD analyses show that all are organic-inorganic hybrids comprising Peacock and Weakley type sandwich-type [Ln(α-XW11O39)2]13−/12‒ (X = SiIV and GeIV) polyanion as the fundamental building block unit. These sandwich type species form polymeric chain assistance with copper organic complexes. These polymeric chains further assemble into 2-D structures by π-π stacking.


Keyword(s)

Polyoxometalates, 3d-4f Heterometallic complexes, Organic-inorganic hybrids, Single crystal XRD


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