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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Time-Resolved EPR and Transient Absorption Studies on Phthalocyaninatosilicon Covalently Linked to Two PROXYL Radicals
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Time-Resolved EPR and Transient Absorption Studies on Phthalocyaninatosilicon Covalently Linked to Two PROXYL Radicals

机译：共价连接两个PROXYL自由基的酞菁硅的时间分辨EPR和瞬态吸收研究

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摘要

By the combined use of electron paramagnetic resonance (EPR) and transient absorption measurements, photophysical properties of tetra-tert-butylphthalocyaninatosilicon (SiPc) covalently linked to two 2,2,5,5-tetramethyl-1-pyrrolidinyloxy (PROXYL) radicals (R2a) have been investigated in terms of the photocontrol of magnetic properties. The steady-state EPR spectrum of R2a indicates that two PROXYL radicals generate a spin-correlated radical pair, where the singlet ground state (S_0') is close to the triplet ground state (T_0'). In time-resolved EPR (TREPR) spectra of R2a, A/E A/E A/E polarizations are initially seen, which then change into E/A E/A E/A polarizations. The initial and later polarizations are reproduced by spin-selective population of the S_0' and T_0' states, respectively. Quantitative analyses of TREPR and transient absorption signals show that the initial A/E A/E A/E polarizations are reproduced by spin-selective relaxation from the excited states, where the SiPc moiety is in the excited singlet state, and that the later E/A E/A E/A polarizations originate from the decay from excited multiplet states consisting of two doublet PROXYLs and SiPc in the excited triplet state.
机译：通过结合使用电子顺磁共振（EPR）和瞬态吸收测量，四叔丁基酞菁硅（SiPc）的光物理性质与两个2,2,5,5-四甲基-1-吡咯烷氧基（PROXYL）共价连接（R2a ）已根据磁特性的光控进行了研究。 R2a的稳态EPR光谱表明，两个PROXYL自由基生成自旋相关的自由基对，其中单线态基态（S_0'）接近三线态基态（T_0'）。在R2a的时间分辨EPR（TREPR）光谱中，首先看到A / E A / E A / E极化，然后变为E / A E / A E / A极化。初始极化和以后的极化分别通过S_0'和T_0'状态的自旋选择性填充来再现。对TREPR和瞬态吸收信号的定量分析表明，初始的A / EA / EA / E极化是通过自旋选择性弛豫从激发态重现的，其中SiPc部分处于激发单重态，而后期的E / AE / AE / A极化源自受激多重态的衰减，该态由两个受激三重态PROXYL和SiPc组成。

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