A homochiral tartrate-bridged dinuclear chromium(iii) complex anion with a resonance-assisted hydrogen bond for proton conduction

Dunatov, Marko; Zhao, Zhibo; Žilić, Dijana; Androš Dubraja, Lidija (2024) A homochiral tartrate-bridged dinuclear chromium(iii) complex anion with a resonance-assisted hydrogen bond for proton conduction. Dalton Transactions, 53 (22). pp. 9315-9322. ISSN 1477-9226

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Abstract

The synthesis of a homochiral building block based on L-tartrate-chromium(III) complex anions is reported. The dinuclear complex anion, which contains two bridging L-tartrate ligands and one aromatic N-donor ligand coordinated to chromium(III) ions, exhibits a boat conformation in which intramolecular resonance-assisted hydrogen bonding is present. The sodium L-tartrate-chromium(III) compound with the formula Na[Cr2(bpy)2(L-tart)2H]·9H2O (1) crystallizes from a methanol–water solution as a high water content material in the monoclinic space group P2. The as-synthesized compound is only stable at high relative humidity and undergoes structural transformations during drying, which are accompanied by water loss. However, these transformations are reversible and upon wetting, the material returns to its high water content structure. Based on a combination of experimental techniques (PXRD, in situ ATR-FTIR and EPR spectroscopy), the structure of the complex anions appears to be insensitive to the humidity variable processes (wetting and drying). Due to the presence of several hydrogen acceptor and donor groups in the L-tartrate-chromium(III) complex anion, we investigated the proton transport properties of a sodium L-tartrate-chromium(III) compound by impedance spectroscopy under dry and wet conditions at different temperatures. Since the relative humidity affects the structural transformations in this system, it also has a large influence on the proton conductivity, which varies by up to four orders of magnitude depending on the degree of hydration. These results confirm that the proton conductivity can be tuned in flexible structures in which non-covalent interactions determine the crystal packing.

Item Type:	Article
Uncontrolled Keywords:	chromium; L-tartarate; proton conductivity; EPR; magnetism
Subjects:	NATURAL SCIENCES > Chemistry
Divisions:	Division of Materials Chemistry Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Metal-organski molekulski materijali kao potencijalni feroelektrici-MOLFERR Lidija Androš Dubraja UIP-2019-04-7433 HRZZ Molekulski magnetizam u naprednim čvrstim i mekim materijalima Dijana Žilić IP-2022-10-9292 Znanstveno-istraživački projekt
Depositing User:	Marko Dunatov
Date Deposited:	06 Sep 2024 08:22
URI:	http://fulir.irb.hr/id/eprint/9067
DOI:	10.1039/d4dt00783b

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