Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 48, Pages 17299-17307Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201502637
Keywords
complete active space (CAS) calculations; EPR spectroscopy; manganese; porphyrinoids; magnetic materials
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Funding
- Spanish MICINN [CTQ2013-44844-P]
- Generalitat Valenciana [PROMETEOII/2014/070, ISIC/2012/002]
- Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy)
- NHMFL - NSF [DMR 1157490]
- State of Florida
- US Department of Energy
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We report on a novel manganese(III)-porphyrin complex with the formula [Mn-III(TPP)(3,5-Me(2)pyNO)(2)]ClO4 center dot CH3CN (2; 3,5-Me(2)pyNO = 3,5-dimethylpyridine N-oxide, H2TPP=5,10,15,20-tetraphenylporphyrin), in which the Mn-III ion is six-coordinate with two monodentate 3,5-Me(2)pyNO molecules and a tetradentate TPP ligand to build a tetragonally elongated octahedral geometry. The environment in 2 is responsible for the large and negative axial zero-field splitting (D = -3.8 cm(-1)), low rhombicity (E/vertical bar D vertical bar = 0.04) of the high spin MO ion, and, ultimately, for the observation of slow magnetic-relaxation effects (E=15.5 cm(-1) at H=1000 G) in this rare example of a manganese-based single ion magnet (SIM). Structural, magnetic, and electronic characterizations were carried out by means of single-crystal diffraction studies, variable-temperature direct- and alternating-current measurements and high-frequency and -field EPR spectroscopic analysis followed by quantum chemical calculations. Slow magnetic-relaxation effects were also observed in the already known analogous compound [Mn-III(TPP)Cl] (1; E-a = 10.5 cm(-1) at H=1000 G). The results obtained for 1 and 2 are compared and discussed herein.
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