High proton conductivity of magnetically ordered 2D oxalate-bridged [MnIICrIII] coordination polymers with irregular topology

Lozančić, Ana; Renka, Sanja; Barišić, Dario; Burazer, Sanja; Molčanov, Krešimir; Pajić, Damir; Jurić, Marijana (2023) High proton conductivity of magnetically ordered 2D oxalate-bridged [MnIICrIII] coordination polymers with irregular topology. Inorganic Chemistry, 62 (24). pp. 9418-9428. ISSN 1520-510X

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Abstract

Two heterometallic coordination polymers {[NH(CH3)2(C2H5)]8[Mn4Cl4Cr4(C2O4)12]}n (1) and {[NH(CH3)(C2H5)2]8[Mn4Cl4Cr4(C2O4)12]}n (2) were obtained by slow evaporation of an aqueous solution containing the building block [A]3[Cr(C2O4)3] [A = (CH3)2(C2H5)NH+ or (CH3)(C2H5)2NH+] and MnCl2·2H2O. The isostructural compounds comprise an irregular two-dimensional (2D) oxalate-bridged anionic layers [Mn4Cl4Cr4(C2O4)12]n8n− with a Shubnikov plane net fes topology designated as (4∙82), interleaved by the hydrogen-bonded templating cations (CH3)2(C2H5)NH+ (1) or (CH3)(C2H5)2NH+ (2). They exhibit remarkable humidity-sensing properties and very high proton conductivity at room temperature [1.60 × 10−3 (Ω·cm)-1 at 90% RH of 1 and 9.6 × 10−4 (Ω·cm)−1 at 94% RH of 2]. The layered structure facilitates the uptake of water molecules, which contributes to the enhancement of proton conductivity at high RH. The better proton transport observed in 1 compared to 2 can be tentatively attributed to the higher hydrophilicity of the cations (CH3)2(C2H5)NH+, which is closely related to the affinity for water molecules. The original topology of the anionic networks in both compounds leads to the development of interesting magnetic phases upon cooling. The magnetically ordered ground state can be described as coupling of ferromagnetic spin chains in which Mn2+ and Cr3+ ions are bridged by bis(bidentate) oxalate groups into antiferromagnetic planes through monodentate-bidentate oxalate bridges in the layers, which are triggered to long-range order below temperature 4.45 K via weaker interlayer interactions.

Item Type:	Article
Additional Information:	This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Inorganic Chemistry, Copyright © 2023 American Chemical Society after peer review. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c00443?articleRef=control
Uncontrolled Keywords:	heterometallic coordination polymer; humidity-sensing property; proton conductivity; magnetically ordered ground state
Subjects:	NATURAL SCIENCES
Divisions:	Division of Materials Chemistry Division of Materials Physics Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Topološka raznolikost oksalatnih spojeva: sinteza, svojstva i upotreba za okside-TOPOXAL-SYPROXID Marijana Jurić IP-2019-04-5742 HRZZ
Depositing User:	Marijana Jurić
Date Deposited:	08 Jan 2025 10:04
URI:	http://fulir.irb.hr/id/eprint/9367
DOI:	10.1021/acs.inorgchem.3c00443

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