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 BPh 4 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)]BPh 4 (1) and two polymorphic modifications (2 and 3) of [Mn(3,5-Br,F-sal 2 323)]BPh 4 . Their crystal structure and magnetic properti...
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Published in | New journal of chemistry Vol. 46; no. 35; pp. 16880 - 16888 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
Published |
12.09.2022
|
Online Access | Get full text |
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Summary: | 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)]BPh
4
(1) and two polymorphic modifications (2 and 3) of [Mn(3,5-Br,F-sal
2
323)]BPh
4
. Their crystal structure and magnetic properties have been studied. The complex [Mn(3,5-diF-sal
2
323)]BPh
4
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)]BPh
4
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. |
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ISSN: | 1144-0546 1369-9261 |
DOI: | 10.1039/D2NJ02872G |