Observation of the First Spin Crossover in an Iron(II) Complex with an S6 Coordination Environment: Tris[bis(N,N-diethylamino)carbeniumdithiocarboxylato]iron(II) Hexafluorophosphate

被引:6
作者
Sugaya, Tomoaki [1 ,4 ]
Fujihara, Takashi [2 ]
Naka, Takashi [3 ]
Furubayashi, Takao [3 ]
Matsushita, Akiyuki [3 ]
Isago, Hiroaki [3 ]
Nagasawa, Akira [1 ]
机构
[1] Saitama Univ, Dept Chem, Grad Sch Sci & Engn, Sakura Ku, 255 Shimo Okubo, Saitama 3388570, Japan
[2] Saitama Univ, Comprehens Anal Ctr Sci, Sakura Ku, 255 Shimo Okubo, Saitama 3388570, Japan
[3] Natl Inst Mat Sci, 1-2-1 Sengen, Tsukuba, Ibaraki 3050047, Japan
[4] Chiba Inst Technol, Educ Ctr, Fac Engn, 2-1-1 Shibazono, Narashino, Chiba 2750023, Japan
关键词
iron; magnetic properties; spin crossover; sulfur; zwitterions; GENERALIZED-GRADIENT-APPROXIMATION; SULFUR DONOR LIGAND; X-RAY CRYSTAL; MOLECULAR-STRUCTURE; MAGNETIC-SUSCEPTIBILITY; VARIABLE-TEMPERATURE; FE(II) COMPLEXES; METAL-COMPLEXES; INNER SALTS; TRANSITION;
D O I
10.1002/chem.201803330
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
For the first time, the spin-crossover (SCO) phenomenon has been observed in an Fe-II-S-6 system in a tris(chelate)-type iron(II) complex with a zwitterionic sulfur donor bidentate, bis(N,N-diethylamino)carbeniumdithiocarboxylate (EtL), [Fe-II(EtL)(3)](PF6)(2) (1), as synthesized by the reaction of a precursor complex [Fe-II(CH3CN)(6)](PF6)(2) with EtL. In the solid state, the high-spin (HS) d(6) state at ambient temperature and the low-spin (LS) d(6) state at temperatures lower than approximately 240 K were evidenced by magnetic measurements with SQUID and Mossbauer spectra in the temperature range 4-290 K. X-ray analyses of the crystals at various temperatures disclosed that the distorted trigonal prismatic coordination environments essentially do not change; however, contraction of Fe-S distances by approximately 10 % (0.22 angstrom), ordering of alkyl groups in EtL and PF6- counteranions, and formation of significant intermolecular S center dot center dot center dot S interactions between adjacent molecules (average distances of 3.59 angstrom) take place during the transition from the HS to the LS state. A large decrease in the volume of the formula unit (78.1 angstrom(3)) might be responsible for the large activation barrier, thereby resulting in a slow phase transition upon cooling.
引用
收藏
页码:17955 / 17963
页数:9
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