Structures and Magnetostructural Correlation of Two Desolvated Polymorphs of Ferrimagnetic meso-Tetrakis(4-chlorophenyl)porphinatomanganese(III) Tetracyanoethenide [MnTClPP]plus[TCNE]•-†
The structures of two polymorphs of [MnTClPP][TCNE] have been determined by Rietveld refinement of the X-ray powder diffraction method. Samples were prepared by thermolysis of the toluene and CH{sub 2}Cl{sub 2} solvates, [MnTClPP][TCNE] {center_dot} 2Sol (Sol = PhMe, CH{sub 2}Cl{sub 2}). The desolvated structures are similar to their solvates, consisting of alternating stacks of the molecular donor and acceptor. Among the four structures, the largest changes are observed for the dihedral angle between the mean Mn(N{sub 4}){sub TPP} and [TCNE]{sup {sm_bullet}-} planes, and the Mn-(N-C){sub TCNE} angle. A magnetostructural correlation between the intrachain coupling and both the dihedral angle between the mean Mn(N{sub 4}){sub TPP} and [TCNE]{sup {sm_bullet}-} planes and Mn-(N-C){sub TCNE} angles is observed. This is in accord with the intrachain coupling arising from the overlap of Mn{sup III} d{sub z{sup 2}}-like singly occupied molecular orbital (SOMO) and the z component of the [TCNE]{sup {sm_bullet}-} {pi}* ({pi}{sub z}*) SOMO, which increases with decreasing dihedral angle between the mean Mn(N{sub 4}){sub TPP} and [TCNE]{sup {sm_bullet}-} planes and Mn-(N-C){sub TCNE} angle.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE SC OFFICE OF SCIENCE (SC)
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 1042229
- Report Number(s):
- BNL-97907-2012-JA; TRN: US201212%%640
- Journal Information:
- Journal of Physical Chemistry C, Vol. 114, Issue 48; ISSN 1932-7447
- Country of Publication:
- United States
- Language:
- English
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