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Geometry and Spin Change at the Heart of a Cobalt(II) Complex: A Special Case of Solvatomorphism
Author(s) -
Cibian Mihaela,
Hanan Garry S.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500852
Subject(s) - tetrahedral molecular geometry , cobalt , hydrogen bond , tetrahedron , spin (aerodynamics) , coordination geometry , molecule , crystallography , chemistry , spin states , ground state , ring (chemistry) , geometry , hydrogen , spectroscopy , materials science , atomic physics , inorganic chemistry , physics , crystal structure , mathematics , quantum mechanics , organic chemistry , thermodynamics
Structural analysis and spectroscopic methods revealed a special case of solvatomorphism: hydrogen‐bonding‐induced geometry and spin change within a same N,O ‐(bis)chelate of cobalt(II). Solid‐state structures are presented for both the tetrahedral and the solvated square‐planar forms of the complex. Magnetic‐moment measurements and ESR spectroscopy confirmed the high‐spin state of the tetrahedral form ( μ eff =4.7 μ B ) and the low‐spin state of the square‐planar solvatomorph. Specific hydrogen‐bonding interactions between the solvent molecules and the complex chelate ring (O1 ⋅⋅⋅ HCHCl 2 ( d =2.26 Å, D =3.24 Å, θ =173°); O2 ⋅⋅⋅ HCHCl 2 ( d =2.22 Å, D =3.19 Å, θ =165°)) play a pivotal role in biasing the system toward the low‐spin ground state.