A Strain-Deformation Nexus within Pincer Ligands: Application to the Spin States of Iron(II) Complexes
| Autor: | Timothy E. Elton, James N. McPherson, Stephen B. Colbran |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Steric effects
Spin states 010405 organic chemistry 010402 general chemistry Ring (chemistry) 01 natural sciences 0104 chemical sciences Pincer movement Inorganic Chemistry chemistry.chemical_compound Crystallography chemistry Spin crossover Chelation Physical and Theoretical Chemistry Homoleptic Terpyridine |
| Zdroj: | Inorganic Chemistry. 57:12312-12322 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.8b02038 |
| Popis: | The substitution of a pyrrolide ring for one (or more) pyridyl rings within the ubiquitous terpyridine (tpy, A) scaffold results in more open geometries of the pyridine–pyrrolide chelate ligands. DFT calculations (B3LYP-GD3BJ/6-31G**) demonstrate that the more open geometries of the unbound ligands are mismatched with the “pinched in” geometries required to chelate transition metal ions (e.g., Zn2+). The strain which builds within these ligands (ΔEL(strain)) as they bind transition metal ions can be related to changes in a single geometric parameter: the separation between the two terminal N atoms (ρ). This relationship applies more generally to other three-ringed tridentate pincer ligands, including those with different donor groups. The approach was applied to homoleptic iron(II) complexes to investigate the contribution of the steric effects operating within the ligands to the different magnetic properties, including spin crossover (SCO) activities, of these systems. |
| Databáze: | OpenAIRE |
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