Mixed-valence {FeFe} hexanuclear complexes with thermally induced Fe() spin-crossover behavior

Cyano-bridged mixed-valence {Fe 6 } hexanuclear complexes {[Tp 4-Me Fe II (CN) 3 ] 2 [Fe III (Tpa)] 2 [Fe III (OR)(Tpa)] 2 }·6ClO 4 · S (Tp 4-Me = tri(4-methyl-pyrazol-1-yl)borate, Tpa = tris(2-pyridylmethyl)amine; R = -CH 3 , S = 8MeOH 1 , R = -C 2 H 5 , S = 6EtOH 2 ) have been obtained by building...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2022-08, Vol.51 (34), p.12968-12974
Main Authors: Jia, Shuwen, Fan, Lingyue, Zheng, Chunyang, Jin, Sai, Li, Dongfeng
Format: Article
Language:English
Subjects:
Crossovers
Ethanol
Magnetic permeability
Single crystals
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Summary:Cyano-bridged mixed-valence {Fe 6 } hexanuclear complexes {[Tp 4-Me Fe II (CN) 3 ] 2 [Fe III (Tpa)] 2 [Fe III (OR)(Tpa)] 2 }·6ClO 4 · S (Tp 4-Me = tri(4-methyl-pyrazol-1-yl)borate, Tpa = tris(2-pyridylmethyl)amine; R = -CH 3 , S = 8MeOH 1 , R = -C 2 H 5 , S = 6EtOH 2 ) have been obtained by building the units of [Tp 4-Me Fe(CN) 3 ] − and [Fe(Tpa)] 2+ in methanol and ethanol, respectively. Complex 1 exhibited single-crystal-to-single-crystal (SCSC) transformation to give {[Tp 4-Me Fe II (CN) 3 ] 2 [Fe III (Tpa)] 2 [Fe III (OH)(Tpa)] 2 }·6ClO 4 ·8H 2 O ( 3 ) in water. Detailed analysis of the coordination environment of the Fe III centers on the square lattice and magnetic susceptibility measurements of all the complexes confirmed their Fe 3+ spin-crossover (SCO) properties ( T 1/2 = 178 K, 1 ; 185 K, 2 ; 208 K, 3 ). Cyano-bridged mixed-valence {Fe 6 } hexanuclear complexes {[Tp 4-Me Fe II (CN) 3 ] 2 [Fe III (Tpa)] 2 [Fe III (OR)(Tpa)] 2 }·6ClO 4 (R = OM, OEt, OH) with Fe 3+ spin-crossover behavior.
ISSN:1477-9226
1477-9234
DOI:10.1039/d2dt02041f