Issue 48, 2023

Improving spin crossover characteristics in heteroleptic [FeIII(qsal-5-I)(qsal-5-OMe)]A complexes

Abstract

A family of heteroleptic spin crossover (SCO) [FeIII(qsal-5-I)(qsal-5-OMe)]A·sol (qsal-5-X = 5-X-2-[(8-quinolylimino)methyl]phenolate; A = NO31 sol = 2MeOH, NCS2 sol = 0.75MeOH·1.3H2O, BF43 sol = MeOH, OTf4, sol = MeOH) complexes have been synthesized. Most of the complexes exhibit gradual SCO, with the exception of NCS, which is principally high spin. In contrast, the OTf complex shows an abrupt hysteretic SCO (35 K) after solvent loss. The magnetic properties of this complex are significantly improved in comparison to the related homoleptics, [Fe(qsal-I)2]OTf 5 (hysteresis, 8 K) and [Fe(qsal-5-OMe)2]OTf·CH2Cl26 (gradual SCO). Structural studies reveal that slight changes in the crystal packing cause stronger interactions improving the cooperativity. These findings are supported by DFT calculations using the r2SCAN functional in which the calculated structures show that SCO from the LS to the HS state causes pronounced scissoring of the 1D π–π chains and substantial changes in their relative orientation following loss of MeOH.

Graphical abstract: Improving spin crossover characteristics in heteroleptic [FeIII(qsal-5-I)(qsal-5-OMe)]A complexes

Supplementary files

Article information

Article type
Paper
Submitted
03 août 2023
Accepted
26 oct. 2023
First published
29 oct. 2023

Dalton Trans., 2023,52, 18148-18157

Improving spin crossover characteristics in heteroleptic [FeIII(qsal-5-I)(qsal-5-OMe)]A complexes

R. Díaz-Torres, S. Gómez-Coca, E. Ruiz, P. Harding and D. J. Harding, Dalton Trans., 2023, 52, 18148 DOI: 10.1039/D3DT02503A

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