Kryman Mark W, Schamerhorn Gregory A, Hill Jacqueline E, Calitree Brandon D, Davies Kellie S, Linder Michelle K, Ohulchanskyy Tymish Y, Detty Michael R
Department of Chemistry, University at Buffalo, The State University of New York , Buffalo, New York 14260-3000, United States.
Institute for Lasers, Photonics and Biophotonics, Department of Chemistry, State University of New York , Buffalo, New York 14260-3000, United States.
Organometallics. 2014 May 27;33(10):2628-2640. doi: 10.1021/om500346j. Epub 2014 May 2.
Analogues of Texas red incorporating the heavy chalcogens S, Se, and Te atoms in the xanthylium core were prepared from the addition of aryl Grignard reagents to appropriate chalcogenoxanthone precursors. The xanthones were prepared via directed metalation of amide precursors, addition of dichalcogenide electrophiles, and electrophilic cyclization of the resulting chalcogenides with phosphorus oxychloride and triethylamine. The Texas red analogues incorporate two fused julolidine rings containing the rhodamine nitrogen atoms. Analogues containing two "half-julolidine" groups (a trimethyltetrahydroquinoline) and one julolidine and one "half-julolidine" were also prepared. The photophysics of the Texas red analogues were examined. The S-analogues were highly fluorescent, the Se-analogues generated single oxygen (O) efficiently upon irradiation, and the Te-analogues were easily oxidized to rhodamines with the telluroxide oxidation state. The tellurorhodamine telluroxides absorb at wavelengths ≥690 nm and emit with fluorescence maxima >720 nm. A mesityl-substituted tellurorhodamine derivative localized in the mitochondria of Colo-26 cells (a murine colon carcinoma cell line) and was oxidized to the fluorescent telluroxide.
通过将芳基格氏试剂添加到适当的硫属元素呫吨酮前体中，制备了在呫吨鎓核心中包含重硫属元素S、Se和Te原子的德克萨斯红类似物。呫吨酮是通过酰胺前体的定向金属化、二硫属元素亲电试剂的添加以及所得硫属元素化物与三氯氧磷和三乙胺的亲电环化反应制备的。德克萨斯红类似物包含两个含有若丹明氮原子的稠合呫吨啶环。还制备了含有两个“半呫吨啶”基团（三甲基四氢喹啉）以及一个呫吨啶和一个“半呫吨啶”的类似物。对德克萨斯红类似物的光物理性质进行了研究。含硫类似物具有高荧光性，含硒类似物在照射时能高效产生活性氧（O），而含碲类似物很容易被氧化为具有碲氧化物氧化态的若丹明。碲代若丹明碲氧化物在波长≥690 nm处有吸收，发射荧光的最大波长>720 nm。一种均三甲苯基取代的碲代若丹明衍生物定位于Colo-26细胞（一种小鼠结肠癌细胞系）的线粒体中，并被氧化为荧光碲氧化物。
