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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photochemistry and Photophysics of (1-Naphthoyl)diphenylphosphine Oxide
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Photochemistry and Photophysics of (1-Naphthoyl)diphenylphosphine Oxide

机译：（1-萘甲酰基）二苯基膦氧化物的光化学和光物理

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摘要

(1-Naphthoyl)diphenylphosphine oxide (1) was synthesized and characterized and its photochemistry investigated using emission spectroscopy, pulse radiolysis, and nanosecond laser flash photolysis. Fluorescence quantum yields are low in aprotic polar and nonpolar solvents. In methanol, as a result of hydrogen-bonding, change of S_1 from an n,#pi#* state to a #pi#,#pi#* state leads to the decrease in the rate constant for intersystem crossing and results, finally, in an increase in fluorescence. Preferential solvation was evaluated using the E_T indicator "Reichardt's dye" (RD). E_T~N values were determined by gradually increasing the concentrations of methanol in methanol/acetonitrile mixtures. Fluorescence quantum yields correlate with the E_T~N values. Photolyiss of 1 yields diphenyl[1-naphthoyl)oxy]phosphine (6), formed mainly via cage recombination of radicals. No radicals were detected by either nanosecond laser flash photolysis or pulse radiolysis of 1 in aprotic solvents. However, photolysis in methanol yields radicals when 1 is excited at 266 nm. The phosphinoyl radical can be quenched by either methyl methacrylate (MMA) or oxygen (k_q = 5.0 * 10~7 and 5.3 * 10~8 M~(-1) s~(-1), respectively). Such radical generation most likely results from the singlet excited state.
机译：合成和表征了（1-萘甲酰基）二苯基膦氧化物（1），并使用发射光谱，脉冲辐射分解和纳秒激光闪光光解研究了其光化学。在质子惰性的极性和非极性溶剂中，荧光量子产率较低。在甲醇中，由于氢键作用，S_1从n，＃pi＃*状态变为#pi＃，＃pi＃*状态导致系统间交叉的速率常数减小，最终，荧光增加。使用E_T指示剂“莱卡特氏染料”（RD）评估优先溶剂化。通过逐渐增加甲醇/乙腈混合物中甲醇的浓度来确定E_T〜N值。荧光量子产率与E_T〜N值相关。 1的Photolyiss产生二苯基[1-萘甲氧基]膦（6），主要是通过自由基的笼型重组形成的。在质子惰性溶剂中，通过纳秒激光闪光光解或1的脉冲辐射分解均未检测到自由基。但是，当1在266 nm激发时，甲醇中的光解会产生自由基。膦酰基可通过甲基丙烯酸甲酯（MMA）或氧气（k_q分别为5.0 * 10〜7和5.3 * 10〜8 M〜（-1）s〜（-1）淬灭。这种自由基的产生很可能是由于单重态激发态。

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