Molecular manipulation of solid state structure: influences of organic components on vanadium oxide architectures

Abstract Among the inorganic materials enjoying widespread contemporary interest, the metal oxide based solid phases occupy a prominent position by virtue of their applications to catalysis, sorption, molecular electronics, energy storage, optical materials and ceramics. The diversity of properties associated with these materials reflects the chemical composition, which allows variations in covalency, geometry and oxidation states, and the crystalline architecture, which may provide different pore structures, coordination sites, or juxtapositions of functional groups. Despite such fundamental and practical significance, the design of the structure of such materials remains a challenge in solid state chemistry. While organic materials have been synthesized which self-assemble into ordered arrays at low temperature and which exhibit molecular recognition and biomimetic activity, the ability to synthesize inorganic materials by rational design remains elusive. Small, soluble molecular building blocks with well-defined reaction chemistries which allow their low-temperature assembly into crystalline solid state inorganic materials are not well known. However, the existence of naturally occurring, structurally complex minerals establishes that hydrothermal synthesis can provide a low temperature pathway to produce open-framework and layered metastable structures utilizing inorganic starting materials. Thus, hydrothermal conditions have been used to prepare microporous tetrahedral framework solids that are capable of shape-selective absorption, like zeolites and aluminophosphates, and more recently in the preparation of complex solid arrays of the M/O/PO3−4 and M/O/RPO2−3 systems (M=V and Mo). The hydrothermal technique may be combined with the introduction of organic components which may act as charge compensating groups, space-filling units, structure directing agents, templates, tethers between functional groups, or conventional ligands in the preparation of inorganic/organic composites. In the past decade, this general strategy has been exploited in the evolution of a family of vanadium oxides incorporating structure-directing organic or secondary-metal organic subunits, which are the topic of this review. The synthetic approach to novel vanadium oxide solids occupies the interface between materials science and coordination chemistry. The emerging theme focuses on the association of an organic component, acting as a ligand, tether, or structure directing moiety, with the inorganic framework of the solid to provide unique composites. While some organic components may limit the size of inorganic cluster subunits of a solid by passivating the surface of an aggregate through capping, such ligands may also serve to link inorganic subunits into complex networks. In other cases, the organic subunit, rather than participating as a covalently bound unit of the framework, acts in a structure directing role, producing amphiphilic materials whose structures are determined by hydrophobic–hydrophilic interactions. This latter feature is reminiscent of the factors influencing biomineralization, a field which may prove relevant to the development of new strategies for the controlled synthesis of organized inorganic and organic/inorganic composite materials. These various approaches to the “design” of inorganic solids are discussed and assessed in terms of the new structural types recently observed in the vanadium oxide chemistry.