Evolution exploration and structure prediction of Keggin-type group IVB metal-oxo clusters

The fascinating chemical structure and broad application prospect of Keggin-type polyoxometalates (POMs) have attracted many chemists to explore and discover continuously. Unlike the traditional Keggin, larger metal atomic radius, higher metal coordinated numbers, lower metal valence states and other features allow the group IVB metal-based Keggin (IVB-Keggin) more space and unknown in terms of structure and performance. Herein, density functional theory (DFT) calculations were performed to explore the influences including cores, shells, caps, and terminal ligands et.al on IVB-Keggin, and analyze the possibility of novel structure synthesis. From the perspective of multi-layer onion-like clusters, molecular energy level, host-guest interaction energy, surface charge and covalent bond polarity can be further adjusted to achieve the oriented design of functional IVB-Keggin. These insights are expected to provide theoretical support for experimental synthesis, opening a new perspective to understand the growth of Keggin