Issue 36, 2024

π-Extended ligands with dual-binding behavior: hindered rotation unlocks unexpected reactivity in cyclometalated Pt complexes

Abstract

Cyclometalated platinum complexes play a crucial role in catalysis, bioimaging, and optoelectronics. Phenylpyridines are widespread cyclometalating ligands that generate stable and highly emissive Pt complexes. While it is common practice to modify these ligands to fine-tune their photophysical properties, the incorporation of polycyclic aromatic hydrocarbons into the ligand's structure has been largely overlooked. This report describes the cyclometalation of naphthalenyl- and anthracenylpyridine ligands, which has resulted in ten new luminescent PtII and PtIV complexes. These species are enabled by a dual-binding behavior discovered in our polyaromatic-containing ligands. The introduction of naphthalenyl and anthracenyl groups unlocks dual binding modes, with the Pt center bonding to either of two distant carbon atoms within the ligand. These complexes exhibit both symmetric structures with two 5-membered metallacycles and asymmetric structures with 5- and 6-membered metallacycles. This work presents a strategy for the regioselective synthesis of Pt complexes with bespoke structures and photophysical properties. Our findings offer new opportunities in platinum chemistry and beyond, with potential implications for materials and technologies.

Graphical abstract: π-Extended ligands with dual-binding behavior: hindered rotation unlocks unexpected reactivity in cyclometalated Pt complexes

Supplementary files

Article information

Article type
Edge Article
Submitted
18 7 2024
Accepted
22 8 2024
First published
11 9 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 14644-14650

π-Extended ligands with dual-binding behavior: hindered rotation unlocks unexpected reactivity in cyclometalated Pt complexes

S. Ota, M. A. Soto, B. O. Patrick, S. Kamal, F. Lelj and M. J. MacLachlan, Chem. Sci., 2024, 15, 14644 DOI: 10.1039/D4SC04799K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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