The role of intermolecular interactions in [Fe(X-salEen)2]ClO4 spin crossover complexes

Marcos A. Bento; Tiago Gomes; Frederico F. Martins; Adrià Gil; Liliana P. Ferreira; Sónia Barroso; Clara S. B. Gomes; Yann Garcia; Paulo N. Martinho

doi:10.1039/D4DT00400K

The role of intermolecular interactions in [Fe(X-salEen)₂]ClO₄ spin crossover complexes†

Marcos A. Bento,^a Tiago Gomes,^a Frederico F. Martins,^b Adrià Gil,

^bc Liliana P. Ferreira,^de Sónia Barroso,‡^fg Clara S. B. Gomes,

^h Yann Garcia

ⁱ and Paulo N. Martinho

*^a

Author affiliations

* Corresponding authors

^a Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal
E-mail: pnmartinho@ciencias.ulisboa.pt

^b BioISI – Biosystems & Integrative Sciences Institute, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal

^c Departament de Química, Física i Ciències Ambientals i del Sòl, ETSEA – Escola Tècnica Superior d'Enginyeria Agrària, Universitat de Lleida, Av. de l'alcalde Rovira Roure, 191, Lleida, Catalunya, Spain

^d Department of Physics, University of Coimbra, 3004-516 Coimbra, Portugal

^e Centro de Física Teórica e Computacional, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, Edifício C8, 1749-016 Lisboa, Portugal

^f UCIBIO, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal

^g i4HB, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal

^h LAQV-REQUIMTE, Department of Chemistry, NOVA School of Science and Technology, NOVA University of Lisbon, 2829-516 Caparica, Portugal

ⁱ Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis (IMCN/MOST), Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium

Abstract

Two new spin crossover (SCO) Fe(III) compounds were prepared, their structures were analysed and their magnetic properties were investigated. An exhaustive analysis of the effects of halogen substitution and aromatic ring functionalisation on the magnetic properties of non-solvated Fe(III) perchlorate complexes has been performed. Through comparative analysis, different magnetic profiles were found for the compounds studied, namely F (1), Cl (2), H (3), Br (4a, 4b), and I (5). Using tools like Hirshfeld analysis, the study revealed patterns in octahedral distortions and deviations from the ideal octahedral geometry. The SCO phenomenon as the conducting wire in this study, emphasises the influence of intermolecular interactions on the low spin (LS) to high spin (HS) transitions in these halogen-substituted complexes. The prevalence of H⋯H contributions has been demonstrated, albeit being the weakest and an inverse strength relationship in H⋯X interactions ranging from F to I. The findings not only interpret the intricate balance between halogen substitution, functionalisation, and intermolecular interactions in modulating magnetic properties but also direct future works in designing similar molecular systems.

Dalton Transactions

The role of intermolecular interactions in [Fe(X-salEen)₂]ClO₄ spin crossover complexes†

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