期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 -, 期 5-6, 页码 730-737出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201201085
关键词
Iron; LIESST effect; Calorimetry; Supramolecular interactions; Spin crossover
资金
- ICREA (Institucio Catalana de Recerca i Estudis Avancats)
- Ministerio de Economia y Competitividad of Spain [CTQ2011-27929-C02-01, MAT2011-24284]
- Royal Golden Jubilee Ph. D Program [PHD/0234/2550]
- Thailand Research Fund
- Khon Kaen University
- Higher Education Research Promotion and National Research University Project of Thailand
- Center of Excellence for Innovation in Chemistry (PERCH-CIC), Office of the Higher Education Commission, Ministry of Education
- ICREA Funding Source: Custom
Reactions of the new, closely related ligands 4,6-dichloro-N,N-di(pyridine-2-yl)-1,3,5-triazine-amine (Cldpat) and 6-chloro-N'-phenyl-N, N-di(pyridin-2-yl)-1,3,5-triazine-2,4-di-amine (Cladpat) with iron(II) thiocyanate produced coordination compounds with drastically distinct magnetic properties. The compound trans-[Fe(Cldpat)(2)(NCS)(2)](H2O) (1) is a high-spin complex from room temperature down to 5 K whereas the analogous compound trans-[Fe(Cladpat)(2)(NCS)(2)] (2) exhibits spin-crossover (SCO) properties with T-1/2 = 178 K. Compounds 1 and 2 (both in its low-spin and high-spin states) have been structurally characterized by X-ray diffraction studies, which revealed identical metal coordination spheres. The SCO properties of 2 have been thoroughly investigated by temperature-dependent magnetic susceptibility measurements and differential scanning calorimetry (DSC), and a LIESST process with rapid relaxation of the trapped HS species has been observed. The equivalent coordination compound with selenocyanate anions, namely [Fe(Cladpat)(2)(NCSe)(2)] (3) also displays SCO properties, although more gradual and with a lower T-1/2 value of 166 K.
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