TY - JOUR
T1 - The role of intermolecular interactions in [Fe(X-salEen)2]ClO4 spin crossover complexes
AU - Bento, Marcos A.
AU - Gomes, Tiago
AU - Martins, Frederico F.
AU - Gil, Adrià
AU - Ferreira, Liliana P.
AU - Barroso, Sónia
AU - Gomes, Clara S. B.
AU - Garcia, Yann
AU - Martinho, Paulo N.
N1 - info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F00100%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F00100%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/LA%2FP%2F0056%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F04046%2F2020/PT#
info:eu-repo/grantAgreement/FCT/Concurso de avaliação no âmbito do Programa Plurianual de Financiamento de Unidades de I&D (2017%2F2018) - Financiamento Programático/UIDP%2F04046%2F2020/PT#
info:eu-repo/grantAgreement/FCT/Concurso de avaliação no âmbito do Programa Plurianual de Financiamento de Unidades de I&D (2017%2F2018) - Financiamento Base/UIDB%2F00618%2F2020/PT#
info:eu-repo/grantAgreement/FCT/Concurso de avaliação no âmbito do Programa Plurianual de Financiamento de Unidades de I&D (2017%2F2018) - Financiamento Programático/UIDP%2F00618%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F50006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/Concurso de avaliação no âmbito do Programa Plurianual de Financiamento de Unidades de I&D (2017%2F2018) - Financiamento Programático/UIDP%2F50006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/LA%2FP%2F0008%2F2020/PT#
info:eu-repo/grantAgreement/FCT//2021.07918.BD/PT#
info:eu-repo/grantAgreement/FCT/CEEC IND 2017/CEECIND%2F00509%2F2017%2FCP1387%2FCT0029/PT#
Funding Information:
This work was supported by the FNRS (PDR T.0095.21, CDR J.0064.23, EQP U.N027.24). The X-ray infrastructure was financed by FCT-MCTES through project RECI/BBBBEP/0124/2012. Sónia Barroso thanks Project SmartBioR for financial support (CENTRO-01-0145-FEDER-000018). Sónia Barroso is also grateful to Centro de Química Estrutural for access to its crystallography facilities. Paulo N. Martinho thanks FCT and RSC for financial support (grants PTDCQUI-QIN0252_2021 (https://doi.org/10.54499/PTDC/QUI-QIN/0252/2021) and R21-7511142525). Adrià Gil is a Serra Húnter Fellow and is very grateful to the Serra Húnter Programme for allowing him to proceed with his research studies. COST Actions CA21101 (COSY) and CA22131 (LUCES) are also acknowledged.
Publisher Copyright:
© 2024 The Royal Society of Chemistry.
PY - 2024/5/21
Y1 - 2024/5/21
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85192693357&partnerID=8YFLogxK
U2 - 10.1039/d4dt00400k
DO - 10.1039/d4dt00400k
M3 - Article
C2 - 38713065
AN - SCOPUS:85192693357
SN - 1477-9226
VL - 53
SP - 8791
EP - 8802
JO - Dalton Transactions
JF - Dalton Transactions
IS - 20
ER -