Abstract
Functional ligand-modified polyoxotitanate (L-POT) cages of the general type [TixOy(OR)z(L)m] (OR = alkoxide, L = functional ligand) can be regarded as molecular fragments of surface-sensitized solid-state TiO2, and are of value as models for studying the interfacial charge and energy transfer between the bound functional ligands and a bulk semiconductor surface. These L-POTs have also had a marked impact in many other research fields, such as single-source precursors for TiO2 deposition, inorganic-organic hybrid material construction, photocatalysis, photoluminescence, asymmetric catalysis and gas adsorption. Their atomically well-defined structures provide the basis for the understanding of structure/property relationships and ultimately for the rational design of new cages targeting specific uses. This highlight focuses on recent advances in L-POTs research, with emphasis on their novel properties and potential applications.
Highlights
Functional ligand-modified polyoxotitanate (L-POT) cages of the general type [TixOy(OR)z(L)m] (OR = alkoxide, L = functional ligand) can be regarded as molecular fragments of surface-sensitized solid-state TiO2, and are of value as models for studying the interfacial charge and energy transfer between the bound functional ligands and a bulk semiconductor surface. These L-POTs have had a marked impact in many other research fields, such as single-source precursors for TiO2 deposition, inorganic– organic hybrid material construction, photocatalysis, photoluminescence, asymmetric catalysis and gas adsorption
In this highlight we focus on recent developments in functional ligand-modified POT cages (L-POTs) of this type, as well as functional ligand-modified M-POT cages (L-M-POTs)
Organic ligands do not always act as sources of detrimental carbon impurities for TiO2 crystallization, but instead can be employed to produce novel hybrid titania materials. This point has been further supported by other recent studies, in which the morphologies of the TiO2 nanostructures formed can be finetuned by varying the type of L-POT precursor employed and the reaction conditions.[36,44]
Summary
Ning Li completed his BEng degree at the National University of Singapore (2009–2013), and undertook a one-year research attachment in the Institute of Materials Research and Engineering A*STAR Singapore, before joining the Wright group as a PhD student in 2014 His current work is on polyoxometalate cage structures and related functional materials. We and others have recently reviewed advances in the area of metal-doped cages (M-POTs), with the emphasis on their structures, photochemistry and applications.[7,9] Apart from metal doping, another major area of interest has been the modification of these POT cages with functional ligands that impart additional structural diversity and chemical reactivity, giving them a broad range of new applications. Models for studying the structural chemistry of bulk TiO2, including its crystal growth mechanism,[10,11] the electronic and structural effects of heterometallic doping,[12,13,14,15,16,17,18,19,20,21] and the influence of surface functional ligand modification.[22,23,24,25,26,27,28,29,30,31] While their excellent solubility in common organic solvents allows POTs to be studied using various standard methods (e.g., NMR,[32,33,34] mass spectrometry35), single-crystal X-ray diffraction is perhaps the preeminent tool for their characterisation (allowing unambiguous characterisation of structural features which can be related to that of bulk TiO2 itself).[9]
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