• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Intersystem Crossing in Diplatinum Complexes
【24h】

Intersystem Crossing in Diplatinum Complexes

机译：双铂配合物中的系统间交叉

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Intersystem crossing (ISC) in solid [(C4H9)(4)N](4)[Pt-2(mu-P2O5(BF2)(2))(4)], abbreviated Pt(pop-BF2), is remarkably slow for a third-row transition metal complex, ranging from tau(ISC) approximate to 0.9 ns at 310 K to tau(ISC) approximate to 29 ns below 100-K A-classical model-based on Boltzmann population of one temperature-independent and two thermally activated pathways was previously employed to account for the ISC rate behavior. An alternative we prefer is to treat Pt(pop-BF2) ISC quantum mechanically, using expressions for multiphonon radiationless transitions. Here we show that a two-channel model with physically plausible parameters can account for the observed ISC temperature dependence. In channel 1, (1)A(2u) intersystem crosses directly into (3)A(2u) using a high energy B-F or P-O vibration as accepting mode, resulting in a temperature-independent ISC rate. In channel 2, ISC occurs via a deactivating state of triplet character (which then rapidly decays to (3)A(2u)), using Pt-Pt stretching (160 cm(-1)) as a distorting mode to provide the energy needed. Fitting indicates that the deactivating state, X-3, is moderately displaced (S = 0.5-3) and blue-shifted (Delta E = 1420-2550 cm(-1)) from (1)A(2u). Our model accounts for the experimental observation that ISC in both temperature independent and thermally activated channels is faster for Pt(pop) than for Pt(pop-BF2): in the temperature independent channel because O-H modes in the former more effectively accept than B-F modes in the latter, and in the thermally activated pathway because the energy gap to X-3 is larger in the latter complex.
机译：固体[（C4H9）（4）N]（4）[Pt-2（mu-P2O5（BF2）（2））（4）]（缩写为Pt（pop-BF2））的系统间穿越（ISC）明显慢对于第三行过渡金属络合物，基于100 K A经典模型，tau（ISC）在310 K时约为0.9 ns，tau（ISC）在29 K以下时约为29 ns。以前采用两种热激活途径来解释ISC速率行为。我们更喜欢的替代方法是使用多声子无辐射跃迁的表达式机械地处理Pt（pop-BF2）ISC量子。在这里，我们显示了具有物理合理参数的两通道模型可以说明观察到的ISC温度依赖性。在通道1中，（1）A（2u）系统间使用高能B-F或P-O振动作为接受模式，直接与（3）A（2u）交叉，从而产生与温度无关的ISC速率。在通道2中，ISC通过三重态字符的停用状态（然后迅速衰减为（3）A（2u））发生，使用Pt-Pt拉伸（160 cm（-1））作为扭曲模式来提供所需的能量。拟合表明，停用状态X-3从（1）A（2u）发生了中等位移（S = 0.5-3）并发生蓝移（Delta E = 1420-2550 cm（-1））。我们的模型说明了实验观察结果，即温度独立通道和热激活通道中的ISC对于Pt（pop）而言要比Pt（pop-BF2）更快：在温度独立通道中，因为前者中的OH模式比BF模式更有效地被接受在后者中以及在热活化路径中，因为在后者复合物中与X-3的能隙更大。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号