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For reviews on spin-crossover effect, see: (a) Topics in Current Chemistry (Spin CrossoVer in Transition Metal Compounds I-III); Gütlich, P., Goodwin, H. A., Eds.; Springer: Berlin/Heidelberg, 2004; Vols. 233-235.
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67949116260
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Synthesis of ligand L was carried out analogous to ref 11. 1H NMR (270 MHz, 25?C, CDCl3): δ ) 6.56 (dd, J ) 1.6, 2.6 Hz, 2 H, pyrazole), 7.83 (d, J ) 1.6 Hz, 2 H, pyrazole), 8.52 (dd, J ) 0.7, 2.6 Hz, 2 H, pyrazole), 9.21 (s, 2 H, pyrazine). In a test tube a solution of ligand L in acetone (0.02 mol/L) was slowly layered on a solution of Co(NO3)2 ·6H2O in acetone (0.02 mol/L). Violet/purple prismatic crystals of 1 appeared after 1 or 2 days. Elemental analysis: observed value (element, theoretical value) ) 30.22% (C, 30.40%), 2.11% (H, 2.04%), 28.11% (N, 28.36%).
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Synthesis of ligand L was carried out analogous to ref 11. 1H NMR (270 MHz, 25?C, CDCl3): δ ) 6.56 (dd, J ) 1.6, 2.6 Hz, 2 H, pyrazole), 7.83 (d, J ) 1.6 Hz, 2 H, pyrazole), 8.52 (dd, J ) 0.7, 2.6 Hz, 2 H, pyrazole), 9.21 (s, 2 H, pyrazine). In a test tube a solution of ligand L in acetone (0.02 mol/L) was slowly layered on a solution of Co(NO3)2 ·6H2O in acetone (0.02 mol/L). Violet/purple prismatic crystals of 1 appeared after 1 or 2 days. Elemental analysis: observed value (element, theoretical value) ) 30.22% (C, 30.40%), 2.11% (H, 2.04%), 28.11% (N, 28.36%).
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0032746324
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Loi, M.1
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Fischer, J.5
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67949111664
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Frisch, M. J. Gaussian 03, revision D.02; Gaussian, Inc.: Wallingford, CT, 2004.
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20
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67949113302
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At the single molecule level, the geometry with dihedral angles N1-Co- O1-O2/N-Co-O3-O4 symmetrically approaching 180°as observed at high temperature is in fact a transition state with an ∼4 kcal/mol barrier between two equivalent potential wells
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At the single molecule level, the geometry with dihedral angles N1-Co- O1-O2/N-Co-O3-O4 symmetrically approaching 180°as observed at high temperature is in fact a transition state with an ∼4 kcal/mol barrier between two equivalent potential wells.
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21
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67949093445
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DFT is a single-reference method and, therefore, less accurate when applied in systems with orbitally near-degenerate ground states such as 1. TDDFT most probably significantly overestimates such small excitation energies.
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DFT is a single-reference method and, therefore, less accurate when applied in systems with orbitally near-degenerate ground states such as 1. TDDFT most probably significantly overestimates such small excitation energies.
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22
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23744446679
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Hayami, S.; Shigeyoshi, Y.; Akita, M.; Inoue, K.; Kato, K.; Osaka, K.; Takata, M.; Kawajiri, R.; Mitani, T.; Maeda, Y. Angew. Chem., Int. Ed. 2005, 44, 4899-4903.
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Hayami, S.1
Shigeyoshi, Y.2
Akita, M.3
Inoue, K.4
Kato, K.5
Osaka, K.6
Takata, M.7
Kawajiri, R.8
Mitani, T.9
Maeda, Y.10
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