Exploring the Magnetic Interactions in Two Novel Cyanide-bridged Homo- and Heterometallic Hexadecanuclear Complexes

Jyoti Yadav; Arindam Gupta; Arpan Mondal; Florian Daumann; Gerald Hörner; Birgit Weber; Sanjit Konar

doi:10.1002/chem.202400321

Exploring the Magnetic Interactions in Two Novel Cyanide-bridged Homo- and Heterometallic Hexadecanuclear Complexes

Chemistry. 2024 Apr 16:e202400321. doi: 10.1002/chem.202400321. Online ahead of print.

Authors

Jyoti Yadav¹, Arindam Gupta², Arpan Mondal², Florian Daumann³, Gerald Hörner³, Birgit Weber⁴, Sanjit Konar⁵

Affiliations

¹ Indian Institute of Science Education and Research Bhopal, Department of Chemistry, Bhauri, Bhopal bypass road, 462066, Bhopal, INDIA.
² Indian Institute of Science Education and Research Bhopal, Chemistry, 462066, Bhopal, INDIA.
³ Friedrich Schiller University Jena, Chemistry, GERMANY.
⁴ Friedrich-Schiller-Universität Jena, Chemistry, GERMANY.
⁵ IISER Bhopal, Department of Chemistry, Indore By Pass Road, 462066, Bhopal, INDIA.

PMID: 38625710
DOI: 10.1002/chem.202400321

Abstract

Two novel isostructural cyanide-bridged hexadecanuclear complexes with the general formula {[Fe(CN)6]6[M{en(Bn)py}]10}2+ [M = Fe (12+), Ni (22+)] have been synthesized. The structural analyses disclose the presence of multivalent Fe centres with different spin states in complex 12+ whereas all the Fe centres share a conserved oxidation state in complex 22+. The DC magnetic study revealed antiferromagnetic interactions between the adjacent metal centres and ferrimagnetic behaviour in 12+. On the other hand, ferromagnetic interactions were observed in complex 22+ due to nearly orthogonal orientation of the interacting orbitals and poor spatial overlap as observed in BS-DFT calculations.

Keywords: Cyanide-bridged; Ferrimagnetic; Magnetic anisotropy; Mössbauer; Supramolecular assembly.