Issue 29, 2024

Controlled crystallisation of porous crystals of luminescent platinum(ii) complexes by electronic tuning of ancillary ligands

Abstract

Porous molecular crystals (PMCs) have gained significant importance as next-generation functional porous materials. However, the selective crystallisation of the PMC phase remains a challenge. Herein, we have systematically controlled the stability of the luminescent PMC phase prepared using the luminescent Pt(II) complex [Pt(pbim)(N^O)] (pbim = 2-phenylbenzimidazolate, N^O = N-heteroaryl carboxylate) with Pt⋯Pt electronic interactions. The PMC phase formation varied significantly among the complexes depending on the heteroaryl group of the ancillary N^O ligand; the oxazolyl-bearing complex did not form a PMC phase, whereas the pyrazyl- and 5-fluoropyridyl-bearing complexes spontaneously formed a porous structure. This difference was rationalised by the π-stacking capability of the heteroaryl group of the ancillary ligand. Furthermore, owing to the presence of the one-dimensional Pt⋯Pt chains in this PMC phase, the photophysical properties of PMCs resulting from the Pt⋯Pt interactions were also significantly changed by the ancillary ligands.

Graphical abstract: Controlled crystallisation of porous crystals of luminescent platinum(ii) complexes by electronic tuning of ancillary ligands

Supplementary files

Article information

Article type
Paper
Submitted
09 Mar 2024
Accepted
09 Apr 2024
First published
09 Apr 2024

Dalton Trans., 2024,53, 12064-12072

Controlled crystallisation of porous crystals of luminescent platinum(II) complexes by electronic tuning of ancillary ligands

T. Mochizuki, M. Yoshida, A. Kobayashi and M. Kato, Dalton Trans., 2024, 53, 12064 DOI: 10.1039/D4DT00713A

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