2021
DOI: 10.1021/acs.cgd.1c00218
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Abundant Solvatomorphism-Tuned Spin Crossover in a Dinuclear Fe(II) Compound: Computational Insights on Molecular Distortion and Packing Effects

Abstract: A series of solvates based on a dinuclear Fe­(II) complex [(TPA)2Fe2(μ-DHBQ)]­[BF4]2·S [S = CH3OH (1·CH 3 OH), 2CH3OH (2·2CH 3 OH), 4DMF (3·4DMF), 2Et2O (4·2Et 2 O), Et2O·MeCN (5·Et 2 O·MeCN), and 2CH2Cl2 (6·2CH 2 Cl 2 )] were synthesized. Upon solvent removal, single-crystal-to-single-crystal (SC-to-SC) transitions could occur for the first four solvates to give 1, 2, 3, and 4·0.5Et 2 O. Within the temperature range of 400–10 K, these compounds exhibited abundant variations in their spin crossove… Show more

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Cited by 6 publications
(6 citation statements)
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“…32 On the other hand, numerous examples of solvatomorphs in SCO complexes have also been reported mainly in the polymeric Fe(II) Hofmann type and in molecular Fe(II) and Fe(III) compounds. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] These solvatomorphs result from a mixture of crystals obtained serendipitously, by a vapor-induced single-crystal-to-single-crystal transformation or growing crystals by liquid-liquid diffusion methods. In the present case, solvatomorphs were obtained by changing the solvent during the recrystallization procedure.…”
Section: Introductionmentioning
confidence: 99%
“…32 On the other hand, numerous examples of solvatomorphs in SCO complexes have also been reported mainly in the polymeric Fe(II) Hofmann type and in molecular Fe(II) and Fe(III) compounds. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] These solvatomorphs result from a mixture of crystals obtained serendipitously, by a vapor-induced single-crystal-to-single-crystal transformation or growing crystals by liquid-liquid diffusion methods. In the present case, solvatomorphs were obtained by changing the solvent during the recrystallization procedure.…”
Section: Introductionmentioning
confidence: 99%
“…5, top). 41 The equilibrium is complete around 170 K, and the material is fully low-spin below that temperature.…”
Section: Resultsmentioning
confidence: 99%
“…ΔH elec was the major factor affecting T c , while the other three terms (ΔH vib , ΔS elec and ΔS vib ) were similar for these halogen-substituted analogs. 35 Isolated Molecules. From a ligand field strength perspective, it is important to note that the F atom possesses greater electronegativity than the Cl atom.…”
Section: Journal Of Thementioning
confidence: 99%
“…These effects can initially perturb subtle energy distinctions between spin states, and their contribution to the energy difference (Δ H ) can be of comparable magnitude to that of Δ H itself. The integration of periodic density functional theory (DFT) calculations augmented with the Hubbard U term and D3 dispersion correction (DFT + U + D 3) has demonstrated greater efficacy and plays a significant role in elucidating the connections between molecular structure and observed properties. , …”
Section: Introductionmentioning
confidence: 99%
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