The Nature of the Spin-State Variation of [FeII(BPMEN)(CH3CN)2](ClO4)2 in Solution
The Nature of the Spin-State Variation of [FeII(BPMEN)(CH3CN)2](ClO4)2 in Solution
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[FeII(BPMEN)(CH3CN)2](ClO4)2 在溶液中自旋态变化的性质
DOI：
10.1002/ejic.200400429
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发表时间：
2005
影响因子：
2.3
通讯作者：
E. P. Talsi
中科院分区：
文献类型：
--
作者：
K. Bryliakov;E. Duban;E. P. Talsi
研究了[FeII（BPMEN）（CH 3CN）2]（ClO 4）2在CD 3CN溶液[低自旋（LS）-高自旋（HS）]中的热致自旋变化行为。变温溶液磁化率测量得到ΔH°LS−HS = 39.7 ± 2.0 kJ·mol−1和ΔS°LS−HS = 135 ± 9 J·mol−1 K−1值。这些值对于纯自旋跃迁来说太高，并且反映了化学过程对自旋跃迁的显著贡献，即检测到一个结合的乙腈分子的解离。因此，LS-HS转换应该被视为与热自旋交叉重叠的化学平衡。由NMR位移随温度的变化估算的整个过程的热力学参数（ΔH° = 40 ± 3 kJ·mol−1，ΔS° = 137 ± 10 J·mol−1 K−1）与由磁化率测量得到的结果完全一致。（© Wiley-VCH Verlag GmbH & Co. KGaA，69451魏因海姆，德国，2005）
Thermally-induced spin variation behavior of [FeII(BPMEN)(CH3CN)2](ClO4)2 in CD3CN solution [low spin (LS)−high spin (HS)] was investigated. Variable temperature solution magnetic susceptibility measurements gave ΔH°LS−HS = 39.7 ± 2.0 kJ·mol−1 and ΔS°LS−HS = 135 ± 9 J·mol−1 K−1 values. These values are too high for a pure spin transition and reflect a significant contribution of chemical processes to the spin transition, namely, the detected dissociation of one bound acetonitrile molecule. Thus, LS−HS conversion should be regarded as a chemical equilibrium overlapped with a thermal spin crossover. The thermodynamic parameters for the overall process estimated from the variation of the NMR shifts with temperature (ΔH° = 40 ± 3 kJ·mol−1, ΔS° = 137 ± 10 J·mol−1 K−1) are in perfect agreement with those obtained by magnetic susceptibility measurements. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
影响因子：
15
作者：
Costas, M;Tipton, AK;Que, L
通讯作者：
Que, L
影响因子：
15
作者：
Chen, K;Costas, M;Que, L
通讯作者：
Que, L