title: Spin crossover phenomenon accompanying order-disorder phase transition in the ligand of [FeII(DAPP)(abpt)](ClO4)2 compound (DAPP = bis(3-aminopropyl)(2-pyridylmethyl)amine, abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole) and its successive self-grinding effect.
abstract: The spin crossover phenomenon of the recently described spin crossover complex [FeII(DAPP)(abpt)](ClO4)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(trs)H = 15.44 kJ mol-1 and Delta(trs)S = 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 ln 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 ln 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)](ClO4)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.
authors.affiliation: Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. miyazaki@chem.sci.osaka-u.ac.jp
authors.forename: Yuji
authors.initials: Y
authors.lastname: Miyazaki
authors.forename: Tadahiro
authors.initials: T
authors.lastname: Nakamoto
authors.forename: Satoaki
authors.initials: S
authors.lastname: Ikeuchi
authors.forename: Kazuya
authors.initials: K
authors.lastname: Saito
authors.forename: Akira
authors.initials: A
authors.lastname: Inaba
authors.forename: Michio
authors.initials: M
authors.lastname: Sorai
authors.forename: Takeo
authors.initials: T
authors.lastname: Tojo
authors.forename: Tooru
authors.initials: T
authors.lastname: Atake
authors.forename: Galina S
authors.initials: GS
authors.lastname: Matouzenko
authors.forename: Samir
authors.initials: S
authors.lastname: Zein
authors.forename: Serguei A
authors.initials: SA
authors.lastname: Borshch