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首页> 外文期刊>Chemical Physics: A Journal Devoted to Experimental and Theoretical Research Involving Problems of Both a Chemical and Physical Nature >Photoinduced nitrosyl linkage isomers in complexes based on the photochromic cation [RuNO(NH3)(5)](3+) with the paramagnetic anion [Cr(CN)(6)](3-) and the diamagnetic anions [Co(CN)(6)](3-) and [ZrF6](2-)
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Photoinduced nitrosyl linkage isomers in complexes based on the photochromic cation [RuNO(NH3)(5)](3+) with the paramagnetic anion [Cr(CN)(6)](3-) and the diamagnetic anions [Co(CN)(6)](3-) and [ZrF6](2-)

机译：基于光致变色阳离子[RuNO（NH3）（5）]（3+）与顺磁性阴离子[Cr（CN）（6）]（3-）和抗磁性阴离子[Co（CN）的配合物中的光诱导亚硝酰基键合异构体（6）]（3-）和[ZrF6]（2-）

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Two metastable nitrosyl linkage isomers SI and SII are generated by light irradiation in the spectral range 370-500 nm in the two diamagnetic compounds [RuNO(NH3)(5)][Co(CN)(6)] and [RuNO(NH3)(5)](2)[ZrF6](3) as well as in the paramagnetic compound [RuNO(NH3)(5)][Cr(CN)(6)]. The frequencies of the v(NO) stretching vibrations of SI and SII identify SI as the isonitrosyl Ru-O-N isomer and SII as the side-on eta(2) isomer of NO. The population, i.e., the number of generated linkage isomers, is determined from the decrease of A the area of the fundamental v(NO) and of the higher harmonic 2 center dot nu(NO) of the nu(NO) stretching vibration of the ground state. Using differential scanning calorimetry (DSC) the heat release during the thermal decay of the metastable linkage isomers is determined. The activation energies, frequency factors, and the energetic position of the metastable linkage isomers are determined from the DSC and infrared spectroscopic experiments. It is found that the exchange of the counter ion significantly influences the energetic positions of the linkage isomers, while the activation energy and frequency factor are much less affected. (C) 2007 Elsevier B.V. All rights reserved.
机译：在两个抗磁性化合物[RuNO（NH3）（5）] [Co（CN）（6）]和[RuNO（NH3）]中，通过在370-500 nm光谱范围内的光照射，生成了两个亚稳态的亚硝酰基键合异构体SI和SII。 （5）]（2）[ZrF6]（3）以及顺磁性化合物[RuNO（NH3）（5）] [Cr（CN）（6）]。 SI和SII的v（NO）拉伸振动的频率将SI识别为异亚硝基Ru-O-N异构体，将SII识别为NO的侧面eta（2）异构体。人口，即产生的键合异构体的数量，是由A的基本v（NO）和nu（NO）的nu（NO）拉伸振动的高次谐波2中心点nu（NO）的面积的减小来确定的。基态。使用差示扫描量热法（DSC），确定了亚稳链异构体热衰变过程中的放热。亚稳态键合异构体的活化能，频率因子和能量位置由DSC和红外光谱实验确定。发现抗衡离子的交换显着影响键合异构体的能量位置，而活化能和频率因子的影响则小得多。 （C）2007 Elsevier B.V.保留所有权利。

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