Linker-dependent control of the chiroptical properties of polymethylene-vaulted trans-bis[(β-iminomethyl)naphthoxy]platinum(ii) complexes

Publication Date

4-3-2024

Document Type

Article

Publication Title

Dalton Transactions

Volume

53

Issue

18

DOI

10.1039/d4dt00273c

First Page

7775

Last Page

7787

Abstract

The effects of polymethylene bridges on the chiroptical properties of trans-bis[(β-iminomethyl)naphthoxy]platinum(ii) platforms were examined both experimentally and theoretically using newly designed planar chiral Pt analogues (1) having three-dimensional superstructures. A series of optically pure polymethylene-vaulted Pt complexes (R)- and (S)-1 were synthesized and characterized with regard to the chiroptical behaviour of the trans-bis[(β-iminomethyl)naphthoxy]platinum(ii) platforms. These complexes were found to exhibit structure-dependent chiroptical characteristics in solution, such that the absolute values of specific rotation, the circular dichroism dissymmetry factor (gabs) and the circularly polarized luminescence dissymmetry factor (glum) all increased upon shortening the polymethylene bridges. Density functional theory and time dependent density functional theory calculations were used to analyse vaulted and non-vaulted complexes, which demonstrated that the present linker-dependent chiroptical properties resulted from constraint-induced changes in the square planar Pt coordination centres rather than from chiral distortion along the coordination platforms.

Funding Number

JP20J11841

Funding Sponsor

Program for Education and Research in Biotechnology, California State University

Department

Chemistry

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