Drastic Effect of Lattice Propionitrile Molecules on the Spin-Transition Temperature of a 2,2鈥?Dipyridylamino/s-triazine-Based Iron(II) Complex

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• 作者：Nanthawat Wannarit ; Nassim Nassirinia ; Saeid Amani ; Norberto Masciocchi ; Sujittra Youngme ; Olivier Roubeau ; Simon J. Teat ; Patrick Gamez
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：September 15, 2014
• 年：2014
• 卷：53
• 期：18
• 页码：9827-9836
• 全文大小：585K
• ISSN：1520-510X

文摘

Reaction of iron(II) selenocyanate (obtained from Fe(ClO₄)₂ and KNCSe) with 2-(N,N-bis(2-pyridyl)amino)-4,6-bis(pentafluorophenoxy)-(1,3,5)triazine (L1^F) in propionitrile produces the compound [Fe(L1^F)₂(NCSe)₂]路2CH₃CH₂CN (1^NCSe路2PrCN), which shows spin-crossover (SCO) properties characterized by a T_1/2 of 283 K and a 螖T₈₀ (i.e., temperature range within which 80% of the transition considered occurs) of about 65 K. Upon air exposure, 1^NCSe路2PrCN gradually converts to a new SCO species that exhibits different properties, as reflected by T_1/2 = 220 K and 螖T₈₀ = 70 K. Various characterization techniques, namely, IR spectroscopy, thermogravimetric analysis, and thermodiffractometric studies, reveal that the new phase is obtained through the loss of the lattice propionitrile molecules within several days upon air exposure or several hours upon heating above 390 K.