Preparation, Characterization And Properties Of Organic-molybdophosphoric Acid Functional Molecular Hybrid Materials

Polyoxometalates (POM) possess good redox properties and structural versatility and have been widely applied in many fields such as medicine, catalysis, and materials sciences. They are also excellent inorganic building blocks for advanced materials. Recently, POMs incorporated with various organic moieties have received increasing attention, because such novel functional hybrid molecules exhibit some interesting properties, such as photochromism, magnetism, photocatalysis, electrocatalysis and third order optical nonlinearities as compared to their bases. To develop rational methods for the modification and functionalization of organic moieties and POM systems can provide the means to chemical, structural and electronic versatility and exploit more fully desirable attributes.In this paper, our interest has been focused on the design and preparation of novel organic-POM charge transfer (CTP) hybrid materials. The acceptor is POM, molybdophosphoric acid with Keggin structure H3PMo12O40 (PMo12), the donors are of electronrich organic compounds with aromatic amines (arylamines) and ferrocenium derivatives. Theπ-πand p-πconjugation system of the organic donors are altered regularly. Eight organic-PMo12 CTP hybrid materials have been synthesized and characterized. The relationship between molecular structure and their properties have been discussed.It mainly contains the issues as follows.1. Four of arylamine-PMo12 hybrid materials were prepared in liquid phase, named as TMB-PMo12, Bzd-PMo12, DMA-PMo12 and Bipy-PMo12, respectively. Another four of ferrocenium derivative-PMo12 hybrid materials were prepared in solid state, named as Fc1-PMo12, Fc2-PMo12, Fc3-PMo12 and Fc4-PMo12, respectively. The configurations of the hybrid materials were confirmed by elemental analysis,...