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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Comparative Photophysics of C_(61)H_2 Isomers
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Comparative Photophysics of C_(61)H_2 Isomers

机译：C_（61）H_2异构体的比较光物理

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摘要

Photophysical properties have been measured and compared for the two known isomers ([6,6]-closed and [5,6]-open) of C_(61)H_2, the parent C_(60) methano adduct. Optical absorption spectra from the ground and triplet states are consistent with C_(60) -electron systems that are significantly less perturbed by [5,6] than [6,6] derivatization. However, intrinsic nonradiative decay of triplet state [5,6]-C_(61)H_2 is the most rapid yet found in any C_(60) adduct, occurring with a characteristic time of 2 μs, a factor of 70 faster than in pristine C_(60). By contrast, the triplet decay time of [6,6]-C_(61)H_2 is 65 μs under the same conditions. The S_1 and T_1 energies of both isomers have been deduced by various methods. It is found that the S_1-T_1 energy gap of [5,6]-C_(61)H_2 is larger than that of C_(60), whereas the opposite relation holds for [6,6]-C_(61)H_2. Quantum yields of triplet state formation and fluorescence were found to be 0.06 and <2 * 10~(-5) for the [5,6] isomer and 0.93 and 7.8 * 10~(-4) for the [6,6] isomer, respectively. The anomalously low quantum yields for [5,6]-C_(61)H_2 indicate efficient nonradiative decay from its S_1 state with a rate constant estimated at ca. 1.5 * 10~(10) s~(-1). It is concluded that isomeric forms of simple C_(60) monoadducts can show major differences in excited-state relaxation.
机译：已测量并比较了母体C_（60）甲醇加合物C_（61）H_2的两个已知异构体（[6,6]-闭合和[5,6]-开放）的光物理性质。来自基态和三重态的光吸收光谱与C_（60）-电子系统一致，C_（60）-电子系统受[5,6]干扰比[6,6]衍生化的干扰少。但是，三重态[5,6] -C_（61）H_2的固有非辐射衰变是在任何C_（60）加合物中发现的最快的，特征时间为2μs，比原始速度快70倍。 C_（60）。相反，在相同条件下，[6,6] -C_（61）H_2的三重态衰减时间为65μs。两种异构体的S_1和T_1能量已通过各种方法推导。发现[5,6] -C_（61）H_2的S_1-T_1能隙大于C_（60）的能隙，而[6,6] -C_（61）H_2的相反关系成立。发现三重态形成和荧光的量子产率对于[5,6]异构体为0.06和<2 * 10〜（-5），对于[6,6]异构体为0.93和7.8 * 10〜（-4） ， 分别。 [5,6] -C_（61）H_2的异常低的量子产率表明，从其S_1状态开始有效的非辐射衰变，其速率常数估计为。 1.5 * 10〜（10）s〜（-1）。结论是，简单的C_（60）单加合物的异构形式可以显示出激发态弛豫的主要差异。

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