The effect of fluorine substituents on the crystal structure and spin crossover behavior of the cation [Mn-III (3,5-diHal-sal(2)323)](+) complex family with BPh4 anions

Mononuclear Mn(III) cation spin-crossover complexes with Schiff base ligands 3,5-diF-sal(2)323 and 3,5-Br,F-sal(2)323 have been synthesized: [Mn(3,5-diF-sal(2)323)]BPh4 (1) and two polymorphic modifications (2 and 3) of [Mn(3,5-Br,F-sal(2)323)]BPh4. Their crystal structure and magnetic properties ha...

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Published inNew journal of chemistry Vol. 46; no. 35; pp. 16880 - 16888
Main Authors Tiunova, A., Kazakova, A., Korchagin, D., Shilov, G., Zakharov, K., Vasiliev, A. N., Yagubskii, E. B.
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 12.09.2022
Royal Society of Chemistry
Subjects
Anions
Bromine
Cations
Chemistry
Chemistry, Multidisciplinary
Crossovers
Crystal structure
Fluorine
Imines
Magnetic properties
Physical Sciences
Science & Technology
Spin transition
MONONUCLEAR MANGANESE(III) COMPLEXES
TRANSITION
STATE
PROFILE
MAGNETIC-PROPERTIES
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Abstract Mononuclear Mn(III) cation spin-crossover complexes with Schiff base ligands 3,5-diF-sal(2)323 and 3,5-Br,F-sal(2)323 have been synthesized: [Mn(3,5-diF-sal(2)323)]BPh4 (1) and two polymorphic modifications (2 and 3) of [Mn(3,5-Br,F-sal(2)323)]BPh4. Their crystal structure and magnetic properties have been studied. The complex [Mn(3,5-diF-sal(2)323)]BPh4 exhibits a gradual and complete spin conversion with T-1/2 = 141 K between high spin (S = 2) and low spin (S = 1) states. Two polymorphic modifications of the complex [Mn(3,5-Br,F-sal(2)323)]BPh4 have fundamentally different magnetic properties: one of the modifications (monoclinic, 2) shows a gradual and complete spin transition with T-1/2 = 137 K, while the other (triclinic, 3) suggests a more abrupt and not complete spin transition at 22 K which is difficult to diagnose due to the competition with the zero-field splitting effects. The magneto-structural relationships were traced in comparison with dichloro-, dibromo- and mixed Br,Cl-substituted [Mn(3,5-R,R'- sal(2)323)] complexes with tetraphenylborate anions.
AbstractList Mononuclear Mn(III) cation spin-crossover complexes with Schiff base ligands 3,5-diF-sal(2)323 and 3,5-Br,F-sal(2)323 have been synthesized: [Mn(3,5-diF-sal(2)323)]BPh4 (1) and two polymorphic modifications (2 and 3) of [Mn(3,5-Br,F-sal(2)323)]BPh4. Their crystal structure and magnetic properties have been studied. The complex [Mn(3,5-diF-sal(2)323)]BPh4 exhibits a gradual and complete spin conversion with T-1/2 = 141 K between high spin (S = 2) and low spin (S = 1) states. Two polymorphic modifications of the complex [Mn(3,5-Br,F-sal(2)323)]BPh4 have fundamentally different magnetic properties: one of the modifications (monoclinic, 2) shows a gradual and complete spin transition with T-1/2 = 137 K, while the other (triclinic, 3) suggests a more abrupt and not complete spin transition at 22 K which is difficult to diagnose due to the competition with the zero-field splitting effects. The magneto-structural relationships were traced in comparison with dichloro-, dibromo- and mixed Br,Cl-substituted [Mn(3,5-R,R'- sal(2)323)] complexes with tetraphenylborate anions.
Mononuclear Mn(iii) cation spin-crossover complexes with Schiff base ligands 3,5-diF-sal2323 and 3,5-Br,F-sal2323 have been synthesized: [Mn(3,5-diF-sal2323)]BPh4 (1) and two polymorphic modifications (2 and 3) of [Mn(3,5-Br,F-sal2323)]BPh4. Their crystal structure and magnetic properties have been studied. The complex [Mn(3,5-diF-sal2323)]BPh4 exhibits a gradual and complete spin conversion with T1/2 = 141 K between high spin (S = 2) and low spin (S = 1) states. Two polymorphic modifications of the complex [Mn(3,5-Br,F-sal2323)]BPh4 have fundamentally different magnetic properties: one of the modifications (monoclinic, 2) shows a gradual and complete spin transition with T1/2 = 137 K, while the other (triclinic, 3) suggests a more abrupt and not complete spin transition at 22 K which is difficult to diagnose due to the competition with the zero-field splitting effects. The magneto-structural relationships were traced in comparison with dichloro-, dibromo- and mixed Br,Cl-substituted [Mn(3,5-R,R′- sal2323)] complexes with tetraphenylborate anions.
Author Tiunova, A.
Zakharov, K.
Vasiliev, A. N.
Kazakova, A.
Korchagin, D.
Yagubskii, E. B.
Shilov, G.
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TRANSITION
STATE
PROFILE
MAGNETIC-PROPERTIES
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Snippet Mononuclear Mn(III) cation spin-crossover complexes with Schiff base ligands 3,5-diF-sal(2)323 and 3,5-Br,F-sal(2)323 have been synthesized:...
Mononuclear Mn(iii) cation spin-crossover complexes with Schiff base ligands 3,5-diF-sal2323 and 3,5-Br,F-sal2323 have been synthesized:...
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SubjectTerms Anions
Bromine
Cations
Chemistry
Chemistry, Multidisciplinary
Crossovers
Crystal structure
Fluorine
Imines
Magnetic properties
Physical Sciences
Science & Technology
Spin transition
Title The effect of fluorine substituents on the crystal structure and spin crossover behavior of the cation [Mn-III (3,5-diHal-sal(2)323)](+) complex family with BPh4 anions
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