Promoting the formation of metal-carboxylate coordination to modulate the dimensionality of ultrastable lead halide hybrids.

Abstract

Crystal engineering of metal halide hybrids is critical to investigate their structure-property relationship and advance their photophysical applications, but there have been limited efforts to employ coordination chemistry to precisely control the dimensionality of metal halide sublattices. Herein, we present a coordination-assembly synthetic strategy developed for the rational modulation of lead halide dimensionality, realizing the transition from 2D to 3D architectures. This manipulation is achieved by utilizing three organocarboxylates featuring the identical cyclohexane backbone unit. Specifically, the 1,4-cyclohexanedicarboxylate and 1,2,4,5-cyclohexanetetracarboxylate ligands facilitate the formation of quasi-2D layered structures, characterized by weakly corrugated and strongly corrugated lead halide layers, respectively. Importantly, the introduction of the 1,2,3,4,5,6-cyclohexanehexacarboxylate ligand results in coordination architectures featuring 3D lead chloride/bromide sublattices. The formation of the 3D coordination architectures templated by the 1,2,3,4,5,6-cyclohexanehexacarboxylate ligand affords extended wavelength coverage and superior carrier transport properties compared to their quasi-2D layered analogues. Importantly, both the 2D and 3D lead halide-based coordination polymers exhibit high aqueous stability over a wide pH range, outperforming the conventional ionic-bound lead halides. Notably, the chemically stable 3D lead bromide exhibits efficient photocatalytic ethylbenzene oxidation with the conversion rate of 498 μmol g-1 h-1, substantially higher than its 2D lead bromide counterparts. This work highlights the important role of coordination chemistry in the rational design of metal halide hybrids, which is crucial for advancing their photophysical properties and applications.