期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 24, 期 63, 页码 16873-16888出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201804161
关键词
facial-meridional; iron; isomers; magnetism; spin transition; thermodynamics
资金
- Swiss National Science Foundation
Chelate coordination of non-symmetrical didentate pyrazine-benzimidazole (L1) or pyridine-benzimidazole (L2) N-donor ligands around divalent iron in acetonitrile produces stable homoleptic triple-helical spin crossover [Fe(Lk)(3)](2+) complexes existing as mixtures of meridional (C-1-symmetry) and facial (C-3-symmetry) isomers in slow exchange on the NMR timescale. The speciation deviates from the expected statistical ratio mer/fac=3:1, a trend assigned to the thermodynamic trans-influence, combined with solvation effects. Consequently, the observed spin state Fe-low-spin(II)<-> Fe-high-spin(II) equilibria occurring in [Fe(Lk)(3)](2+) refer to mixtures of complexes in solution, an issue usually not considered in this field, but which limits rational structure-properties correlations. Taking advantage of the selective and quantitative formation of isostructural facial isomers in non-constrained related spin crossover d-f helicates (HHH)-[LnFe(Lk)(3)](5+) (Ln is a trivalent lanthanide, Lk=L5, L6), we propose a novel strategy for assigning pertinent thermodynamic driving forces to each spin crossover triple-helical isomer. The different enthalpic contributions to the spin state equilibrium found in mer-[Fe(Lk)(3)](2+) and fac-[Fe(Lk)(3)](2+) reflect the Fe-N bond strengths dictated by the trans-influence, whereas a concomitant solvent-based entropic contribution reinforces the latter effect and results in systematic shifts of the spin crossover transitions toward higher temperature in the facial isomers.
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