Heteroleptic iron(III) Schiff base spin crossover complexes: halogen substitution, solvent loss and crystallite size effects

Wasinee Phonsri, David S Macedo, Casey G. Davies, Guy N L Jameson, Boujemaa Moubaraki, Keith S Murray

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The influence of the halogen substituent on the qsal moiety of iron(iii) heteroleptic compounds with the formulae [Fe(qsal-X)(thsa)]·nMeCN, where qsal-X- = X-substituted quinolylsalicylaldimine; thsa2- = thiosemicarbazone-salicylaldiminate; X = F; n = 2.5, 1·2.5MeCN and X = Cl 2, Br 3 and I 4, n = 1 (labelled 2·MeCN, 3·MeCN and 4·MeCN, respectively) has been systematically investigated. Magnetic studies on solid samples show incomplete spin crossover in 1-3 which can be related to MeCN solvent loss. Complex 4·MeCN remains fully LS up to 360 K. Single crystals have been examined at variable temperatures for samples possessing different degrees of solvation. Intermolecular C-X⋯H interactions are present for X = F, Cl and Br while a C-I⋯π interaction is uniquely observed in 4·MeCN. These preferential interactions result in different supramolecular packings of the various halogen substituted compounds. However, as the LS stability increases from F to I, the ligand field strength is then also suggested to increase from F to I. Consequently, in this family, the electronic structure resulting from halogen variation is believed to influence the magnetic properties more than crystal packing effects. Mössbauer spectra, at variable temperatures, confirm the presence of Fe(iii) and the magnetic properties in these compounds. The effect of different drying methods as well as the crystal/powder effect on the magnetic properties are discussed in the case of 2·MeCN.

Original languageEnglish
Pages (from-to)7020-7029
Number of pages10
JournalDalton Transactions
Volume46
Issue number21
DOIs
Publication statusPublished - 2017

Cite this

Phonsri, Wasinee ; Macedo, David S ; Davies, Casey G. ; Jameson, Guy N L ; Moubaraki, Boujemaa ; Murray, Keith S. / Heteroleptic iron(III) Schiff base spin crossover complexes : halogen substitution, solvent loss and crystallite size effects. In: Dalton Transactions. 2017 ; Vol. 46, No. 21. pp. 7020-7029.
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abstract = "The influence of the halogen substituent on the qsal moiety of iron(iii) heteroleptic compounds with the formulae [Fe(qsal-X)(thsa)]·nMeCN, where qsal-X- = X-substituted quinolylsalicylaldimine; thsa2- = thiosemicarbazone-salicylaldiminate; X = F; n = 2.5, 1·2.5MeCN and X = Cl 2, Br 3 and I 4, n = 1 (labelled 2·MeCN, 3·MeCN and 4·MeCN, respectively) has been systematically investigated. Magnetic studies on solid samples show incomplete spin crossover in 1-3 which can be related to MeCN solvent loss. Complex 4·MeCN remains fully LS up to 360 K. Single crystals have been examined at variable temperatures for samples possessing different degrees of solvation. Intermolecular C-X⋯H interactions are present for X = F, Cl and Br while a C-I⋯π interaction is uniquely observed in 4·MeCN. These preferential interactions result in different supramolecular packings of the various halogen substituted compounds. However, as the LS stability increases from F to I, the ligand field strength is then also suggested to increase from F to I. Consequently, in this family, the electronic structure resulting from halogen variation is believed to influence the magnetic properties more than crystal packing effects. M{\"o}ssbauer spectra, at variable temperatures, confirm the presence of Fe(iii) and the magnetic properties in these compounds. The effect of different drying methods as well as the crystal/powder effect on the magnetic properties are discussed in the case of 2·MeCN.",
author = "Wasinee Phonsri and Macedo, {David S} and Davies, {Casey G.} and Jameson, {Guy N L} and Boujemaa Moubaraki and Murray, {Keith S}",
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Heteroleptic iron(III) Schiff base spin crossover complexes : halogen substitution, solvent loss and crystallite size effects. / Phonsri, Wasinee; Macedo, David S; Davies, Casey G.; Jameson, Guy N L; Moubaraki, Boujemaa; Murray, Keith S.

In: Dalton Transactions, Vol. 46, No. 21, 2017, p. 7020-7029.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Heteroleptic iron(III) Schiff base spin crossover complexes

T2 - halogen substitution, solvent loss and crystallite size effects

AU - Phonsri, Wasinee

AU - Macedo, David S

AU - Davies, Casey G.

AU - Jameson, Guy N L

AU - Moubaraki, Boujemaa

AU - Murray, Keith S

PY - 2017

Y1 - 2017

N2 - The influence of the halogen substituent on the qsal moiety of iron(iii) heteroleptic compounds with the formulae [Fe(qsal-X)(thsa)]·nMeCN, where qsal-X- = X-substituted quinolylsalicylaldimine; thsa2- = thiosemicarbazone-salicylaldiminate; X = F; n = 2.5, 1·2.5MeCN and X = Cl 2, Br 3 and I 4, n = 1 (labelled 2·MeCN, 3·MeCN and 4·MeCN, respectively) has been systematically investigated. Magnetic studies on solid samples show incomplete spin crossover in 1-3 which can be related to MeCN solvent loss. Complex 4·MeCN remains fully LS up to 360 K. Single crystals have been examined at variable temperatures for samples possessing different degrees of solvation. Intermolecular C-X⋯H interactions are present for X = F, Cl and Br while a C-I⋯π interaction is uniquely observed in 4·MeCN. These preferential interactions result in different supramolecular packings of the various halogen substituted compounds. However, as the LS stability increases from F to I, the ligand field strength is then also suggested to increase from F to I. Consequently, in this family, the electronic structure resulting from halogen variation is believed to influence the magnetic properties more than crystal packing effects. Mössbauer spectra, at variable temperatures, confirm the presence of Fe(iii) and the magnetic properties in these compounds. The effect of different drying methods as well as the crystal/powder effect on the magnetic properties are discussed in the case of 2·MeCN.

AB - The influence of the halogen substituent on the qsal moiety of iron(iii) heteroleptic compounds with the formulae [Fe(qsal-X)(thsa)]·nMeCN, where qsal-X- = X-substituted quinolylsalicylaldimine; thsa2- = thiosemicarbazone-salicylaldiminate; X = F; n = 2.5, 1·2.5MeCN and X = Cl 2, Br 3 and I 4, n = 1 (labelled 2·MeCN, 3·MeCN and 4·MeCN, respectively) has been systematically investigated. Magnetic studies on solid samples show incomplete spin crossover in 1-3 which can be related to MeCN solvent loss. Complex 4·MeCN remains fully LS up to 360 K. Single crystals have been examined at variable temperatures for samples possessing different degrees of solvation. Intermolecular C-X⋯H interactions are present for X = F, Cl and Br while a C-I⋯π interaction is uniquely observed in 4·MeCN. These preferential interactions result in different supramolecular packings of the various halogen substituted compounds. However, as the LS stability increases from F to I, the ligand field strength is then also suggested to increase from F to I. Consequently, in this family, the electronic structure resulting from halogen variation is believed to influence the magnetic properties more than crystal packing effects. Mössbauer spectra, at variable temperatures, confirm the presence of Fe(iii) and the magnetic properties in these compounds. The effect of different drying methods as well as the crystal/powder effect on the magnetic properties are discussed in the case of 2·MeCN.

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U2 - 10.1039/c7dt00947j

DO - 10.1039/c7dt00947j

M3 - Article

VL - 46

SP - 7020

EP - 7029

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

SN - 1477-9226

IS - 21

ER -