Bottom-up synthesis strategy of a two-dimensional {Fe5} cluster-based coordination polymer: stepwise formation of a {Fe5} cluster and its dimension augmentation

Abstract

Sophisticated aggregation assembly is challenging in assembly chemistry. Monitoring the assembly process helps to understand the assembly mechanism and create new building blocks. A two-dimensional (2D) cluster-based coordination polymer (CP) of {Fe₅}-2D was developed by hierarchical dimension augmentation from its one-dimensional (1D) cluster-based CP of {Fe₅}-1D and discrete zero-dimensional (0D) cluster of {Fe₅}-0D. A stepwise formation of the {Fe₅}-0D cluster could be further monitored by time-dependent high-resolution electrospray ionization mass spectrometry and five reaction intermediate fragments were screened. A possible bottom-up synthesis mechanism for this cluster-based CP was proposed as [Fe₁] → [Fe₂] → [Fe₃] → [Fe₄] → {Fe₅}-0D → {Fe₅}-1D → {Fe₅}-2D.