CIS-TRANS PHOTOISOMERIZATION IN RU(BPY)2(OH2)22+ - CRYSTAL-STRUCTURE OF TRANS-[RU(BPY)2(OH2)(OH)](CLO4)2
CIS-TRANS PHOTOISOMERIZATION IN RU(BPY)2(OH2)22+ - CRYSTAL-STRUCTURE OF TRANS-[RU(BPY)2(OH2)(OH)](CLO4)2
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DOI：
10.1021/ja00522a026
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
MEYER, TJ
中科院分区：
文献类型：
--
作者：
DURHAM, B;WILSON, SR;MEYER, TJ
研究了Ru（bpy）_2（OH_2）_（2+）在酸性水溶液中的顺反光异构化反应。反应与辐射波长无关，量子产率为0.043（顺-反）和0.025（反-* 顺）。在ClO-t-存在下，Ru（bpy）_2（OF_2）_2 ~（2+）被光化学氧化为Ru（bpy）_2（OH_2）（OH）_2 ~+，该反应的量子效率与[ClO_4 ~]成线性关系。异构化和氧化反应被解释为通过解离途径发生的，该解离途径是由位于最低lyingd-d态之上的最低lyingmetal-ligand电荷转移态的热布居引起的。用三维X射线计数器数据测定了/A3 ztt-[Ru（bpy）2（0 H2）0 H]（C104）2的晶体结构。该配合物的晶体结构为三角晶系，空间群为P3 I21，晶胞尺寸为a= 10.902（2），c= 17.070（4）。该结构已被细化到传统的R因子的最终值为0.031的基础上，2259独立观察。配合物的几何构型大致为八面体，Ru-N键为2.090（3）和2.099（3）A。Ruatom位于一个双重轴上，这限制了两个配位的氧原子是等价的;与水配体形式上缔合的另外的氢原子与相邻离子上的羟基配体形成对称的氢键。Ru-O距离为2.007（3）A。
The cis— trans photoisomerization of Ru (bpy) 2 (OH2) 22+ in acidic aqueous solution has been investigated. The re-action is independent of the wavelength of irradiation and occurs with quantumyields of 0.043 (cis-» trans) and 0.025 (trans-* cis). In the presence of ClO-t-the photochemical oxidationof Ru (bpy) 2 (OFl2) 22+ to Ru (bpy) 2 (OH2)(OH) 2+ occurs and the quantum efficiency for this reaction is linearly dependent on [C104~]. The isomerization and oxidation reactions are inter-preted as occurring by a dissociative pathway which results from the thermal population of a low lyingd-d state which lies above a lowest lyingmetal-ligand charge-transfer state. The crystal structure of/A3ztt-[Ru (bpy) 2 (0H2) 0H](C104) 2 has been determined from three-dimensional X-ray counter data. The complex crystallizes in the trigonal space group P3I21 with three formula units in a cell of dimensions a= 10.902 (2), c= 17.070 (4) A. The structure has been refined to a final value of the conventional R factor of 0.031 based on 2259 independent observations. The geometry of the complex is roughly octahedral, with Ru-N bonds of 2.090 (3) and 2.099 (3) A. The Ruatom lies on a twofold axis, which constrains the two coordinated oxy-gen atoms to be equivalent; the additional hydrogen atom formally associated with the water ligand forms a symmetrical hydrogen bond to the hydroxyl ligand on an adjacent ion. The Ru-O distance is 2.007 (3) A.