Issue 14, 2025

Charge transfer between a metal-bound halide and a quinone through π-hole interactions leads to bulk conductivity

Abstract

π-Hole interactions between a metal-bound halide and a quinoid ring are described in four novel isostructural co-crystals with the formula [Cu(terpy)ClX]·X′4Q (terpy = 2,2′:6′,2′′-terpyridine; Q = quinone; X = Br, I; X′ = Cl, Br). An unusually strong π-hole interaction between Cu–X and the quinoid ring is noted. Periodic DFT computations estimate the energy of the X⋯quinone interaction to be −20.79 kcal mol−1, indicating a very strong non-covalent interaction attributed to a higher degree of polarization along the bonding path. The black colour of the crystals originates from a cooperative intermolecular charge transfer between the [Cu(terpy)ClX] complex and the quinone π-system, with iodine playing a dominant role in this process by facilitating the π-hole interaction that enhances the charge transfer mechanism. All the compounds are considered to be weak semiconductors with the σDC magnitude ranging between 10−11 and 10−9 S cm−1. It is anticipated that by a smart choice of electron donors and electron acceptors, one can substantially enhance the effect and engineer more efficient conductive materials.

Graphical abstract: Charge transfer between a metal-bound halide and a quinone through π-hole interactions leads to bulk conductivity

Supplementary files

Article information

Article type
Paper
Submitted
23 Oct 2024
Accepted
19 Feb 2025
First published
03 Mar 2025
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2025,54, 5796-5804

Charge transfer between a metal-bound halide and a quinone through π-hole interactions leads to bulk conductivity

L. Molčanov, A. Krawczuk, L. Pavić, M. Jurić, L. Androš Dubraja and K. Molčanov, Dalton Trans., 2025, 54, 5796 DOI: 10.1039/D4DT02961E

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