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

Molčanov, Lidija; Krawczuk, Anna; Pavić, Luka; Jurić, Marijana; Androš Dubraja, Lidija; Molčanov, Krešimir (2025) Charge transfer between a metal-bound halide and a quinone through π-hole interactions leads to bulk conductivity. Dalton Transactions, 54 (14). pp. 5796-5804. ISSN 1477-9226

PDF - Published Version - article Available under License Creative Commons Attribution Non-commercial. Download (1MB)

Abstract

pi-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 pi-hole interaction between Cu-X and the quinoid ring is noted. Periodic DFT computations estimate the energy of the X & ctdot;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 pi-system, with iodine playing a dominant role in this process by facilitating the pi-hole interaction that enhances the charge transfer mechanism. All the compounds are considered to be weak semiconductors with the sigma DC 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.

Item Type:	Article
Uncontrolled Keywords:	charge transfer; crystal engineering; quantum crystallography; quinones; pi-holes; semiconductors
Subjects:	NATURAL SCIENCES > Interdisciplinary Natural Sciences
Divisions:	Division of Materials Chemistry Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Primjena dvoelektronske multicentrične veze i jake interakcije pi-šupljine u kristalnom inženjerstvu i dizajnu materijala Krešimir Molčanov IP-2024-05-8711 HRZZ Topološka raznolikost oksalatnih spojeva: sinteza, svojstva i upotreba za okside-TOPOXAL-SYPROXID Marijana Jurić; Lidija Kanižaj; Damir Pajić; Pavla Šenjug IP-2019-04-5742 HRZZ
Depositing User:	Krešimir Molčanov
Date Deposited:	14 Apr 2025 13:32
URI:	http://fulir.irb.hr/id/eprint/9694
DOI:	10.1039/D4DT02961E

Actions (login required)

View Item