Water-Soluble Pentagonal-Prismatic Titanium-Oxo Clusters

By using solubility control to crystallize the prenucleation clusters of hydrosol, a family of titanium-oxo clusters possessing the {Ti18O27} core in which the 18 Ti­(IV)-ions are uniquely connected with μ-oxo ligands into a triple-decked pentagonal prism was obtained. The cluster cores are wrapped by external sulfate and aqua ligands, showing good solubilities and stabilities in a variety of solvents including acetonitrile and water and allowing their solution chemistry being studied by means of electrospray ionization mass spectroscopy, 17O NMR, and vibrational spectroscopy. Furthermore, this study provides new titanium oxide candidates for surface modifications and homogeneous photocatalysis.通过溶解度调控（solubility control）策略实现水溶胶（hydrosol）预成核簇（prenucleation clusters）的结晶，本研究成功获得一系列具有{Ti18O27}核心的钛氧簇（titanium-oxo clusters）家族。该核心中的18个四价钛离子（Ti(IV)）通过μ-氧配体（μ-oxo ligands）独特连接，构筑为三层五角棱柱（triple-decked pentagonal prism）结构。簇合物核心被外部硫酸根配体（sulfate ligands）与水配体（aqua ligands）包覆，在乙腈（acetonitrile）、水等多种溶剂中展现出优异的溶解性与稳定性，可通过电喷雾电离质谱法（electrospray ionization mass spectroscopy）、氧-17核磁共振波谱法（17O NMR）及振动光谱法（vibrational spectroscopy）对其溶液化学行为开展研究。此外，本研究为表面修饰与均相光催化（homogeneous photocatalysis）领域提供了新型钛氧化物候选材料。