Synthesis and Properties of Heavy Chalcogen Analogues of the Texas Reds and Related Rhodamines
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- 作者：Mark W. Kryman ; Gregory A. Schamerhorn ; Jacqueline E. Hill ; Brandon D. Calitree ; Kellie S. Davies ; Michelle K. Linder ; Tymish Y. Ohulchanskyy ; Michael R. Detty
- 刊名：Organometallics
- 出版年：2014
- 出版时间：May 27, 2014
- 年：2014
- 卷：33
- 期：10
- 页码：2628-2640
- 全文大小：614K
- 年卷期：v.33,no.10(May 27, 2014)
- ISSN：1520-6041
文摘
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 鈥渉alf-julolidine鈥?groups (a trimethyltetrahydroquinoline) and one julolidine and one 鈥渉alf-julolidine鈥?were also prepared. The photophysics of the Texas red analogues were examined. The S-analogues were highly fluorescent, the Se-analogues generated single oxygen (1O2) efficiently upon irradiation, and the Te-analogues were easily oxidized to rhodamines with the telluroxide oxidation state. The tellurorhodamine telluroxides absorb at wavelengths 鈮?90 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 in vitro to the fluorescent telluroxide.