ABSTRACT Conjugated thioketone and thioketone S-oxide (sulfine) were synthesized from the corresponding ketone conjugated to a 1,3-butadiene system incorporated in a dibenzobarrelene skeleton. The conjugated thioketone was obtained by the reaction of the corresponding diazo compound with elemental sulfur, the oxidation of which with m-chloroperoxybenzoic acid provided the conjugated sulfine as a mixture of (Z)- and (E)-stereoisomers. (E)-Sulfine gradually isomerized to (Z)-sulfine in solution in the dark. Photoisomerization between (Z)- and (E)-sulfines was observed under photoirradiation together with the desulfurization to the corresponding ketone. The conjugated thioketone showed the weak long-wavelength absorption at 626 nm due to the n-π* excitation in the optical absorption spectrum and nonphotoluminescent. The conjugated (Z)-sulfine exhibited the long-wavelength absorption at 448 nm due to the π-π* excitation and very weak photoluminescence at 489 nm with the quantum yield of 0.002 at room temperature. The weak photoluminescence was enhanced in EtOH at 77 K showing yellow luminescence, and the quantum yield increased to 0.32. Lifetime values of the luminescence (2.4 and 6.8 ns) at 77 K suggests that the luminescence is fluorescence. A large solvent effect and a similar temperature dependency of photoluminescence were observed for the conjugated ketone. GRAPHICAL ABSTRACT

中文翻译：

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共轭硫酮、硫酮 S-氧化物 (Sulfine) 和相关化合物的合成和光物理性质并入二苯甲茚骨架

摘要 共轭硫酮和硫酮 S-氧化物（亚砜）是由相应的酮与 1,3-丁二烯系统共轭合成的，并结合在二苯甲茚骨架中。共轭硫酮是通过相应的重氮化合物与元素硫反应得到的，元素硫用间氯过氧苯甲酸氧化得到共轭亚砜，它是 (Z)-和 (E)-立体异构体的混合物。(E)-亚砜在黑暗中的溶液中逐渐异构化为 (Z)-亚砜。在光照射下观察到 (Z)- 和 (E)-亚砜之间的光异构化以及脱硫为相应的酮。由于光吸收光谱中的 n-π* 激发和非光致发光，共轭硫酮在 626 nm 处显示出弱的长波长吸收。由于 π-π* 激发和 489 nm 处非常微弱的光致发光，共轭 (Z)-亚砜在 448 nm 处表现出长波长吸收，室温下量子产率为 0.002。弱光致发光在 77 K 的 EtOH 中增强，显示黄色发光，量子产率增加到 0.32。77 K 下的发光寿命值（2.4 和 6.8 ns）表明发光是荧光。对于共轭酮，观察到大的溶剂效应和光致发光的类似温度依赖性。图形概要 量子产率增加到0.32。77 K 下的发光寿命值（2.4 和 6.8 ns）表明发光是荧光。对于共轭酮，观察到大的溶剂效应和光致发光的类似温度依赖性。图形概要 量子产率增加到0.32。77 K 下的发光寿命值（2.4 和 6.8 ns）表明发光是荧光。对于共轭酮，观察到大的溶剂效应和光致发光的类似温度依赖性。图形概要