Unknown

Dataset Information

0

Crystallographic Detection of the Spin State in FeIII Complexes.


ABSTRACT: We report a single example of thermal spin crossover in a series of FeIII complexes, [FeIII(R-sal2323)]+, which typically stabilize the low-spin (S = 1/2) state. Single-crystal X-ray diffraction analysis of 53 such complexes with varying "R" groups, charge-balancing anions, and/or lattice solvation confirms bond lengths in line with an S = 1/2 ground state, with only the [FeIII(4-OMe-sal2323)]NO3 complex (1a) exhibiting longer bond lengths associated with a percentage of the spin sextet form at room temperature. Structural distortion parameters are investigated for the series. A magnetic susceptibility measurement of 1a reveals a gradual, incomplete transition, with T 1/2 = 265 K in the solid state, while Evans method NMR reveals that the sample persists in the low-spin form in solution at room temperature. Computational analysis of the spin state preferences for the cations [FeIII(4-OMe-sal2323)]+ and [FeIII(sal2323)]+ confirmed the energetic preference for the spin doublet form in both, and the thermal spin crossover in complex 1a is therefore attributed to perturbation of the crystal packing on warming.

SUBMITTER: Kelly CT 

PROVIDER: S-EPMC9634697 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature

altmetric image

Publications

Crystallographic Detection of the Spin State in Fe<sup>III</sup> Complexes.

Kelly Conor T CT   Griffin Michael M   Esien Kane K   Felton Solveig S   Müller-Bunz Helge H   Morgan Grace G GG  

Crystal growth & design 20221017 11


We report a single example of thermal spin crossover in a series of Fe<sup>III</sup> complexes, [Fe<sup>III</sup>(R-sal<sub>2</sub>323)]<sup>+</sup>, which typically stabilize the low-spin (<i>S</i> = 1/2) state. Single-crystal X-ray diffraction analysis of 53 such complexes with varying "R" groups, charge-balancing anions, and/or lattice solvation confirms bond lengths in line with an <i>S</i> = 1/2 ground state, with only the [Fe<sup>III</sup>(4-OMe-sal<sub>2</sub>323)]NO<sub>3</sub> complex (  ...[more]

Similar Datasets

| S-EPMC11384930 | biostudies-literature
| S-EPMC9813924 | biostudies-literature
| S-EPMC9631739 | biostudies-literature
| S-EPMC5609531 | biostudies-literature
| S-EPMC6900076 | biostudies-literature
| S-EPMC8927127 | biostudies-literature
| S-EPMC4358629 | biostudies-literature
| S-EPMC9313551 | biostudies-literature
| S-EPMC2942906 | biostudies-literature
| S-EPMC10251414 | biostudies-literature