期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 111, 期 43, 页码 12508-12517出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp0730287
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The spin crossover phenomenon of the recently described spin crossover complex [FeII(DAPP)(abpt)](CIO4)(2) [DAPP = bis(3-aminopropyl)(2-pyridylmethyl)amine, abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole] accompanying an order-disorder phase transition of the ligand was investigated by adiabatic heat capacity calorimetry, far-IR, IR, and Raman spectroscopies, and normal vibrational mode calculation. A large heat capacity peak due to the spin crossover transition was observed at T-trs = 185.61 K. The transition enthalpy and entropy amounted to Delta H-trs = 15.44 U mol(-1) and Delta S-trs = 83.74 J K-1 mol(-1), respectively. The transition entropy is larger than the expected value 60.66 J K-1 mol(-1), which is contributed from the spin multiplicity (R In 5; R: the gas constant), disordering of the carbon atom of the six-membered metallocycle in the DAPP ligand, and one of the two perchlorate anions (2R In 2), and change of the normal vibrational modes between the high-spin (HS) and low-spin (LS) states (35.75 J K-1 mol(-1)). The remaining entropy would be ascribed to changes of the lattice vibrations and molecular librations between the HS and LS states. Furthermore, [Fe(DAPP)(abpt)j(CIO4)(2) crystals disintegrated and became smaller crystallites whenever they experienced the phase transition. This may be regarded as a successive self-grinding effect, evidenced by adiabatic calorimetry, DSC, magnetic susceptibility, and microscope observation. The relationship between the crystal size and the physical quantities is discussed.
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