3-(3-thienyl)-4,4-di(3-thienyl)-8-(3-thienyl)-4-bora-3a,4a-diaza-s-indacene | 1000779-00-9

• 英文名称: 3-(3-thienyl)-4,4-di(3-thienyl)-8-(3-thienyl)-4-bora-3a,4a-diaza-s-indacene
• CAS: 1000779-00-9
• 化学式: C₂₅H₁₇BN₂S₄
• 分子量: 484.498
• InChiKey: WNJMXEFMMIDOGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  3-thienyl lithium 、 4,4-difluoro-8-(3-thienyl)-4-bora-3a,4a-diaza-s-indacene 以 四氢呋喃 为溶剂， 以8.5%的产率得到3-(3-thienyl)-4,4-di(3-thienyl)-8-(3-thienyl)-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  Cu²⁺ Colorimetric Sensing and Fluorescence Enhancement and Hg²⁺ Fluorescence Diminution in “Scorpionate”-like Tetrathienyl-Substituted Boron−Dipyrrins

  摘要：

  Four novel tetrathienyl-substituted boron-dipyrrin-type (BODIPY-type) complexes, 3-(R')-4+di(R')-8-R-4-bora3a,4a-diaza-s-indacene (4a, R = 2-T, R' = 2-T; 4b, R = 3-T, R' = 2-T; 5a, R = 2-T, R' = 3-T; 5b, R = 3-T, R' = 3-T; T = thienyl) have been prepared and fully characterized to explore patterns of stoichiometric Mn+ recognition in solution. Treatment of the respective parent BF2 dipyrrin with 2- or 3-thienyllithium gave the unexpected asymmetric tetrathienyl-substituted products in 8.5-35% yield. Compounds 4a and 4b bear a neutral "scorpionate"like [SSS] tridentate binding pocket. Extensive NMR and UV-vis spectroscopic studies were performed on 4a-5b; 5a, 4b, and 5b were structurally characterized. The Phi(F) values for 4a-5b all decrease compared to the BF2-containing parent molecules (0.00058, 0.012, 0.00090, and 0.0051, respectively), with lambda(abs,max) values (is an element of, M-1 cm(-1)) of 563 (44 000), 553 (29 000), 539 (33 000), and 531 (44 000) nm, respectively, and Stokes' shifts of 25-36 nm. Upon treatment with metal ion (Ca2+, CS+, Mn2+, CO2+, Cu2+, Ag+, Zn2+, Cd2+, Hg2+, Pb2+) perchlorate salts, the solution of 4b undergoes rapid pink-to-clear switch-off behavior upon Cu2+ addition (10 mu M scale) with smaller effects seen for 4a. Further, there were 2- to 19-fold Cu2+ fluorescence enhancements for these ligands. Cu2+ and Hg2+-L (L = 4a-5b) binding was modeled, and response patterns for Mn+-L 1:1 molar solutions upon Cu2+ addition were measured. Upon treatment with Hg2+, all ligand solutions show a significant fluorescence decrease accompanied by minor absorption increases. The UV-vis spectroscopic detection limit for Cu2+ and Hg2+ is similar to 270 ppb and similar to 1.7 ppm, respectively; the naked eye detection limit for Cu2+ with 4b (1.0 x 10(-5) M) is similar to 23 mu M. DFT calculations gave HOMO-LUMO gaps of 478 (4a), 462 (4b), 448 (5a), and 442 nm (5b). Molecular orbital diagrams for 4a-5b revealed that the HOMO and LUMO electron density is distributed onto the 3-position-thienyl group and to a lesser degree the B(thienyl)(2) moiety.

  DOI：

  10.1021/ic701101j