Pt-S Bond-Enabled Temperature-Dependent Phosphorescence in S-Heteroaryl Tetradentate Pt(S^C^N^O) Complexes

Feng Zhan; Guo-Liang Lin; Teng-Shuo Zhang; Kewei Xu; Yun-Fang Yang; Guijie Li; Yuanbin She

doi:10.1021/acs.inorgchem.4c00601

Pt-S Bond-Enabled Temperature-Dependent Phosphorescence in S-Heteroaryl Tetradentate Pt(S^C^N^O) Complexes

Inorg Chem. 2024 May 13;63(19):8822-8831. doi: 10.1021/acs.inorgchem.4c00601. Epub 2024 May 2.

Authors

Feng Zhan¹, Guo-Liang Lin¹, Teng-Shuo Zhang¹, Kewei Xu¹, Yun-Fang Yang¹, Guijie Li¹, Yuanbin She¹

Affiliation

¹ College of Chemical Engineering, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, PR China.

PMID: 38696545
DOI: 10.1021/acs.inorgchem.4c00601

Abstract

This study presents the rare examples of S-heteroaryl tetradentate Pt(S^C^N^O) luminescent complexes (PtSZ and PtSZtBu) containing a Pt-S bond. The presence of the Pt-S bond allows the novel Pt(S^C^N^O) complexes to exhibit temperature-dependent phosphorescent emission behavior. The PtSZtBu exhibits dual-emission phenomena and biexponential transient decay spectra above 250 K, indicating the presence of two minimal excited states in the potential energy surface (PES) of the T₁ state. Through complementary experimental and computational studies, we have identified changes in orbital composition between Pt(d_xy)-S(p_x) and Pt(d_yz)-S(p_z) in excited states with increasing temperature. This results in two energy minima, enabling the excited states to decay selectively and radiatively at different temperatures. Consequently, this leads to remarkable steady-state and transient emission spectra changes. Our work not only provides valuable insights for the development of novel Pt-S bond-based tetradentate Pt(II) complexes but also enhances our understanding of the distinctive properties governed by the Pt-S bond.