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The molecular and supramolecular aspects in mononuclear manganese(iii) Schiff-base spin crossover complexes.

Authors :
Wang, Shi
Li, Ya-Juan
Ju, Fei-Fei
Xu, Wu-Tan
Kagesawa, Koichi
Li, Yong-Hua
Yamashita, Masahiro
Huang, Wei
Source :
Dalton Transactions: An International Journal of Inorganic Chemistry. 9/7/2017, Vol. 46 Issue 33, p11063-11077. 15p.
Publication Year :
2017

Abstract

Manganese(iii) hexadentate Schiff base complexes ([Mn(sal-N-1,5,8,12)]Y·S, Y = AsF6 (1); Y = SbF6 (2); Y = NO3, S = C2H5OH (3) and Y = Cl (4)) have been investigated to determine the impact of anion effects, intramolecular ligand distortions, and intermolecular supramolecular structures on the spin crossover (SCO) behavior. The crystal structure of [Mn(sal-N-1,5,8,12)]PF6, a complex known to exhibit an abrupt SCO behavior with an 8 K hysteresis window, reveals that this complex has a temperature-dependent anion order–disorder transition that disrupts the hydrogen-bonding chain upon SCO, indicating that hydrogen bonds between cations and anions greatly influence the magnetic properties. The SCO in 1 is mediated by intermolecular hydrogen-bonding interactions. The subtle balance of these hydrogen bonds induces a cooperative SCO process with a hysteresis width of 18 K, which is the largest one reported in the d4 SCO chemistry. For 2, crystal structural analysis indicates that changing the anion from AsF6− to SbF6− led to close stackings between phenyl groups from ligands. These stackings preclude the spin transition of the [Mn(sal-N-1,5,8,12)]+ cations. With NO3− and Cl− as counterions, the [Mn(sal-N-1,5,8,12)]+ cations are arranged more loosely and exhibit gradual SCO in the temperature range of 300–100 K. Careful evaluation of the supramolecular structures of these complexes and similar complexes reported previously revealed strong correlation between the supramolecular packing forces and their magnetic properties. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
14779226
Volume :
46
Issue :
33
Database :
Academic Search Index
Journal :
Dalton Transactions: An International Journal of Inorganic Chemistry
Publication Type :
Academic Journal
Accession number :
124770691
Full Text :
https://doi.org/10.1039/c7dt01718a