One-Pot and Postsynthetic Phenol-Thermal Synthesis toward Highly Stable Titanium-Oxo Clusters

The synthetic approach plays a crucial role for the exploration and optimization of functional materials. As the molecular models of titanium dioxide, polyoxo-titanium clusters have undergone rapid development over past decade. Unfortunately, many of them are unstable, especially in aqueous environments, greatly limiting their applications in catalysis and environmental fields. In this work, we report a novel phenol-thermal approach toward the construction of highly stable polyoxo-titanium clusters. In addition to the traditional one-pot procedure, the phenol-thermal synthesis can also be used as a postsynthetic pathway to modify the alcohol terminated titanium-oxo clusters. During the modification in phenol, Ti-O core structures consisting entirely of 6-coordinated Ti^IV centers can be retained. Nevertheless, isopropanol terminated 5-coordinated Ti^IV centers are not stable and reconstructed to 6-coordinated Ti^IV centers during the phenol-thermal modification to form new Ti-O clusters. Physical attribute studies confirm that the obtained phenolic clusters generally display much better stability and stronger visible light absorption than isopropanol stabilized clusters with identical or similar cores. Therefore, phenol can not only offer a suitable solution environment for the construction of new cluster structures but also provide robust protection for the cluster cores and also an efficient method to enhance their visible light responses.