硼芳基和硼炔基Aza-BODIPY类近红外荧光染料的设计、合成与性质研究
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摘要
近二十年，发展起来荧光染料Aza-BODIPY (如化合物1)，受到人们的广泛关注。Aza-BODIPY衍生物有其独特的光谱特性：吸收与发射波长较长,荧光量子产率较高,光稳定性好，对pH不敏感等[1-4]。因此，对其结构进行修饰能够改善其荧光性能,可以潜在应用于化学传感器、荧光开关、离子检测、光动力学疗法等领域，具有优异的药理活性和医用前景[5-9]，成为近年来研究的热点。
本论文基于Aza-BODIPY1（简写为F-Aza-BODIPY）作为染料前体，主要设计合成硼原子上用芳基或炔基修饰的两个系列的染料分子，其中芳基双取代的衍生物简称C-Aza-BODIPY，炔基双取代的衍生物简称E-Aza-BODIPY，分别用芳基和炔基两个取代基得到的不对称取代的衍生物简称C/E-Aza-BODIPY。首先采用简便易行的路线合成了四苯基Aza-BODIPY做为染料前体，通过芳基或炔基格氏试剂处理，得到F修饰的目标产物。合成过程中，通过控制F-Aza-BODIPY和格氏试剂的比例来得到对称或不对称双取代的目标染料分子。
为了探究F修饰的衍生物的性质特点，对其进行各种表征测试。紫外吸收和荧光发射光谱测试发现目标产物的荧光量子产率有不同程度降低；在不同pH溶液中的稳定性测试，显示目标产物比染料前体在强碱性环境中有更高的稳定性；根据电化学循环伏安计算的HOMO-LUMO轨道能隙值与其的吸收波长位移相吻合；X-射线单晶衍射确认其结构；通过荧光共聚焦成像确定此类近红外荧光染料有良好的透膜性，可以进行细胞染色。
Among the recent twenty years, Aza-BODIPY(eg. compd.1) as a family offluoresencence dyes has been attracting increasing interest. Aza-BODIPYs possesses distinctfluorescence characters, such as long absorption and emission wavelength, high molar extinctioncoefficient, high photostability, high stability at physiological conditions and so on. Modificationson the structures to improve their fluorescent performance, have led to potential applications inchemosensor, fluorescent switch, photosencitizer of photodynamic therapy, controllablefluorescence chemosensor and near infrared fluorescent probe and so on.
Based on the parent compound Aza-BODIPY1, three series of Aza-BODIPY dyes weredesigned and synthsized. F-Aza-BODIPY as one of the most studied Aza-BODIPY dye wasselected as our target family. The modifications of1on boron atom were very straight forward. C-and E-Aza-BODIPYs can be made through nucleophilic attack of Grignard reagent. During thepreparation, by means of controlling the equivalence of Gridard reagent over Aza-BODIPY,products2-4can be obtained. Aza-BODIPY with two different subsitutients on boron atom4canbe obtained by judicious control of the equivalence of two different Gridard reagents.
To better understand the discrepancy of structure and characteristic between the targetproduct and parent product, UV-Visible absorption and fluorescence spectra, stability underdifferent solutions of pH1-14, cyclic voltammetry of electrochemistry were measured; thestructures of compounds were analyzed by X-ray single crystal diffraction; Fluorescencemicroscope imaging was also carried out.
本论文基于Aza-BODIPY1（简写为F-Aza-BODIPY）作为染料前体，主要设计合成硼原子上用芳基或炔基修饰的两个系列的染料分子，其中芳基双取代的衍生物简称C-Aza-BODIPY，炔基双取代的衍生物简称E-Aza-BODIPY，分别用芳基和炔基两个取代基得到的不对称取代的衍生物简称C/E-Aza-BODIPY。首先采用简便易行的路线合成了四苯基Aza-BODIPY做为染料前体，通过芳基或炔基格氏试剂处理，得到F修饰的目标产物。合成过程中，通过控制F-Aza-BODIPY和格氏试剂的比例来得到对称或不对称双取代的目标染料分子。
为了探究F修饰的衍生物的性质特点，对其进行各种表征测试。紫外吸收和荧光发射光谱测试发现目标产物的荧光量子产率有不同程度降低；在不同pH溶液中的稳定性测试，显示目标产物比染料前体在强碱性环境中有更高的稳定性；根据电化学循环伏安计算的HOMO-LUMO轨道能隙值与其的吸收波长位移相吻合；X-射线单晶衍射确认其结构；通过荧光共聚焦成像确定此类近红外荧光染料有良好的透膜性，可以进行细胞染色。
Among the recent twenty years, Aza-BODIPY(eg. compd.1) as a family offluoresencence dyes has been attracting increasing interest. Aza-BODIPYs possesses distinctfluorescence characters, such as long absorption and emission wavelength, high molar extinctioncoefficient, high photostability, high stability at physiological conditions and so on. Modificationson the structures to improve their fluorescent performance, have led to potential applications inchemosensor, fluorescent switch, photosencitizer of photodynamic therapy, controllablefluorescence chemosensor and near infrared fluorescent probe and so on.
Based on the parent compound Aza-BODIPY1, three series of Aza-BODIPY dyes weredesigned and synthsized. F-Aza-BODIPY as one of the most studied Aza-BODIPY dye wasselected as our target family. The modifications of1on boron atom were very straight forward. C-and E-Aza-BODIPYs can be made through nucleophilic attack of Grignard reagent. During thepreparation, by means of controlling the equivalence of Gridard reagent over Aza-BODIPY,products2-4can be obtained. Aza-BODIPY with two different subsitutients on boron atom4canbe obtained by judicious control of the equivalence of two different Gridard reagents.
To better understand the discrepancy of structure and characteristic between the targetproduct and parent product, UV-Visible absorption and fluorescence spectra, stability underdifferent solutions of pH1-14, cyclic voltammetry of electrochemistry were measured; thestructures of compounds were analyzed by X-ray single crystal diffraction; Fluorescencemicroscope imaging was also carried out.
引文
[1](a)Barone, P. W.; Parker, R. S.; Strano, M. S. Anal. Chem.,2005,77,7556.(b) Kiyose, K.; Kojima, H.;Nagano, T. Chem. Asia. J.,2008,50,515.
[2](a)Harriman, A.; Mallon, L. J.; Goeb, S.; Ziessel, R. Chem. Phys.,2007,9,5199.(b) Yamada, K.;Nomura, Y.; Citterio, D.; Iwasawa, N.; Suzuki, K. J. Am. Chem. Soc.,2005,127,6956.(c)Wang,J.;Qian, X. Org. Lett.,2006,8,3721.(d)Hudnall, T.W.;Gabbai,F. P. Chem. Commun.,2008,4596.(e)Domaille, D.W.; Zeng, L.; Chang,C. J. J. Am. Chem. Soc.,2010,132,1194.(f) Atilgan, E.; Ozdemir,E.;Akkaya, E. U. Org. Lett.,2010,12,4792.
[3] Patterson, G. H. Science,2003,300,87.
[4] Khodjakov, A. Science,2003,300,91.
[5]陈小利，李翠红，宋庆宝.浙江化工，2010,41,18.
[6] Qin, W.; Barush, M.; Stefan, A.; Auweraer, M. V.; Boens, N. Chem. Phys.,2005,6,2343.
[7] Cox, R. D.; Vernon, D. I.; Griffiths, J.; Brown, S. Photochem. Photobiol.,2002,75,392.
[8] Coskun, A.; Akkaya, E. U. Tetra. Lett.,2004,45,4947.
[9] Wagner, R. W.; Lindsey, J. S. Pure.Appl. Chem.,1996,68,1373.
[10] Schulman S G． Fluorescence and Phosphorescence Spectroscopy. Physicochemical Principles andPractic．New York：oxford,1977．
[11]陈国珍，黄贤智，许金钩．荧光分析法(第二版)．北京：科学出版社，1900．
[12]张华山，王红，赵媛嫒．分子探针与检测试剂．北京：科学出版社，2002．
[13]西川秦治，平木敬三．分析化学译刊，1987．
[14] Haugland R P．Handbook of Fluorescent Probes and Research Chemicals．6th ed．1996．
[15] Strekowski L, Lee H, Lin S. J. Org. Chem.,2000,65(22)：7703-7705.
[16] Zhang Z, Achilefu S. Org. Lett.,2004,6,2067-2070.
[17] Mishra, Behera R K，Behera P K et a1. A Review. Chem. Rev.,2000，100(6)：1973-2012.
[18] Wu Y，Peng X，Guo B et a1. Org. Biomol. Chem.,2005,3,1387-1392.
[19] Takakusa B，Kikuchi K, Urano Y et a1. J. Am. Chem. Soc.,2002,124,1653-1657.
[20] Rogers, M. A. T. J. Chem. Soc.,1943,590.
[21] Zhang Y, Yang R H, Liu Fet a1. Anal. Chem.,2006,76,7336-7345.
[22] Gawronski J, Gawronska K, Skowronek P et a1. J. Org. Chem.,1999,64,234-241.
[23] Woodroofe C C, Lippard S J. J. Am. Chem. Soc.,2003,125,11458-11459.
[24] Karolin J, Johansson L B, Strandberg L et a1. J. Am. Chem. Soc.,1994,116,7801-7806.
[25] Meltola N J, Soini A E, Hanninen P E. Journal of Fluorescence,2004,14,129-138．
[26]刘欣，王红，张华山.分析科学学报，2001，17，346.
[27] Karolin, J.; Johansson, L. B.; Strandberg, L. J. Am. Chem. Soc.,1994,116,7801.
[28] McDonnell, S. O,; Hall, M. J.; Allen, L. T. J. Am. Chem. Soc.,2005,127,16360.
[29] Gallagher, W. M.; Allen, L. T.; O'Shea, C. J. Cancer,2005,92,1702.
[30] O'Shea, D.; Killoran, J.; Gallagher, W. US,7220732[P].2007.
[31] Armin Burghart, Heejin Kim, Kevin Burgess et a1. J. Org. Chem.,1999,64,7813-7819.
[32] Weili Zhao, Erick Carreira. Angew. Chem. Int. Ed.,2005,117,1705-1707.
[33] Treibs A, Kreuzer F H. Angew. Chem. Int. Ed.,1968,718,208-216.
[34] Worries H J, Koek J H. Recl. Tray. Chim. Pays-Bas.1985,104,288-291.
[35] Haugland R P, Kang H C. US4774339.1988.
[36] Kang R C. WO93/09185.1993.
[37] Haugland R P, Kang H C. US5433896.1995.
[38] Zhao W, Carreira E M. Angew. Chem. Int. Ed.,2005,44,1677-1679.
[39] Ulrich G, Goze C, Guardigli M et a1. Angew. Chem. Int. Ed.,2005,44,3694.
[40] Kim H, Burghart A,Welch M B et a1., Chem. Comun.,1999,1889-1890.
[41] Cben J, Burghart A, Kovacs A et a1. J. Org. Chem.,2000,65,2900-2906.
[42] Chen J, Burghart A, Wan C. Tetrahedron Letters,2000,41,2303-2307.
[43] Chen J, Reibenspies J, Derecskei-Kovacs et a1. Chem. Commun.,1999,2501-2502.
[44] Loudet A,Bandichhor R,Burgess K.et.al. Org.Lett.,2008,10,4771-4774
[45] Palma A, Tasior M, Frimansson D.O.et.al. Org.Lett.,2009,11,3638-3641
[46] Xin-Dong Jiang, Jian Zhang,Taniyuki Furuyama,and Weili Zhao. Org.Lett.,2012,14,248-251
[47] Chouaib Tahtaoui, Marcel Hibert.et.al.J. Org. Chem.,2007,72:269-272.
[48] Travis Lundrigan, Alison Thompson.et.al. Chem. Commun.,2012,48,1003-1005.
[49] Christine Goze, Gilles Ulrich. et.al. J. Am. Chem. Soc.,2006,128,10231
[50] Barthram, A. M.; Cleary, R. L.; Kowallick, R.; Ward, M. D. Chem. Commun.,1998,2695.
[51](a) Ntziachristos, V.; Ripoll, J.; Weissleder, R. Opt. Lett.,2002,27,333.(b) Sowell, J.; Strekowski, L.;Patonay, G. J. Biomed. Opt.,2002,7,571.
[52](a) Haugland, R. P.; Spence, M. T. Z.; Johnson, I. D.; Basey, A. The Handbook: A Guide toFluorescent Probes and Labeling Technologies,10th ed.; Molecular Probes: Eugene, OR,2005.(b)Karolin, J.; Johansson, L. B.-A.; Strandberg, L.; Ny, T. J. Am. Chem. Soc.,1994,116,7801.(c) Wan,C.-W.; Burghart, A.; Chen, J.; Bergstrom, F.; Johanson, L. B.-A.; Wolford, M. F.; Kim, T. G.; Topp,M. R.; Hochstrasser, R. M.; Burgess, K. Chem. Eur. J.,2003,9,4430.
[53] Chen, J.; Burghart, A.; Derecskei-Kovacs, A.; Burgess, K. J. Org. Chem.2000,65,2900.
[54](a) Umezawa, K.; Nakamura, Y.; Makino, H.; Citterio, D.; Suzuki, K. J. Am. Chem. Soc.,2008,130,1550.(b) Umezawa, K.; Matsui, A.; Nakamura, Y.; Citterio, D.; Suzuki, K. Chem. Eur. J.,2009,15,1096.(c) Awuah, S. G.; Polreis, J.; Biradar, V.; You, Y. Org. Lett.,2011,13,3884.
[55](a) Killoran, J.; Allen, L.; Gallagher, J.; Gallagher, W.; O’Shea, D. F. Chem. Commun.,2002,1862.(b)Gorman, A.; Killoran, J.; O’Shea, C.; Kenna, T.; Gallagher, W. M.; O’Shea, D. F. J. Am. Chem. Soc.,2004,126,10619.(c) McDonnell, S. O.; Hall, M. J.; Allen, L. T.; Byrne, A.; Gallagher, W. M.;O’Shea, D. F. J. Am. Chem. Soc.,2005,127,16360.(d) Killoran, J.; O’Shea, D. F. Chem. Commun.,2006,1503.
[56] Goze, C.; Ulrich, G.; Ziessel, R. J. Org. Chem.,2007,72,313.
[57](a) Goze, C.; Ulrich, G.; Ziessel, R. Org. Lett.,2006,8,4445.(b) Ulrich, G.; Goze, C.; Goeb, S.;Retailleau, P.; Ziessel, R. New J. Chem.,2006,30,9822.(c) Goeb, S.; Ziessel, R. Org. Lett.,2007,9,737.(d) Bonardi, L.; Ulrich, G.; Ziessel, R. Org. Lett.,2008,10,2183.(e) Ulrich, G.; Goze, C.;Guardigli, M.; Roda, A.; Ziessel, R. Angew. Chem., Int. Ed.2005,44,3694.
[58] Palma, A.; Tasior, M.; Frimannsson, D. O.; Vu, T. T.; Méallet-Renault, R.; O’Shea, D. F. Org. Lett.,2009,11,3638.
[59] Jiang, X.-D.; Zhang, J.; Fukuyama, T.; Zhao, W. Org. Lett.,2012,14,248.
[60](a) Loudet, A.; Bandichhor, R.; Burgess, K.; Palma, A.; McDonnell, S. O.; Hall, M. J.; O’Shea, D. F.Org. Lett.,2008,10,4771.(b) Yakubovskyi, V. P.; Shandura, M. P.; Kovtun, Y. P. Synth. Commun.,2010,40,944.
[61](a) Li, Y.; Patrick, B. O.; Dolphin, D. J. Org. Chem.,2009,74,5237.(b) Descalzo, A. B.; Rurack, K.Chem.-Eur. J.,2009,15,3173.(c) Kubo, Y.; Yoshida, K.; Adachi, M.; Nakamura, S.; Maeda, S. J. Am.Chem. Soc.,1991,113,2868.(d) Barthram, A. M.; Cleary, R. L.; Kowallick, R.; Ward, M. D. Chem.Commun.,1998,2695.(e) Li, H.; Nguyen, N.; Fronczek, F. R.; Vicente, M. G. H. Tetrahedron,2009,65,3357.
[62](a) Jiang, X.-D.; Zhang, J.; Shao, X.; Zhao, W. Org. Biomol. Chem.,2012,10,1966.(b) Zhao, W.;Carreira, E. M. Angew. Chem., Int. Ed.2005,44,1677.(c) Zhao, W.; Carreira, E. M. Chem. Eur. J.,2006,12,7254.
[63] Goze, C.; Ulrich, G.; Mallon, L. J.; Allen, B. D.; Harriman, A.; Ziessel, R. J. Am. Chem. Soc.,2006,128,10231.
[64]9和10的部分键角()和键长(°): N1-C1,1.403(3); N1-C2,1.352(3); N2-C3,1.407(3); N2-C4,1.353(3); N1-B,1.586(3); N2-B,1.580(3); C5-B,1.636(3); C6-B,1.616(3); C1-N1-C2,107.8(2);C1-N1-B,122.7(2); C2-N1-B,128.7(2); C3-N2-C4,107.6(2); C3-N2-B,122.7(2); C4-N2-B,127.7(2);N1-B-N2,104.6(2); N1-B-C5,108.8(2); N2-B-C6,110.9(2); C5-B-C6,115.0(2).: N1-C1,1.409(4);N1-C2,1.360(4); N2-C3,1.395(4); N2-C4,1.360(4); N1-B,1.562(5); N2-B,1.561(5); F5-B,1.365(5);F6-B,1.377(5); C1-N1-C2,106.9(3); C1-N1-B,121.5(3); C2-N1-B,130.9(3); C3-N2-C4,107.0(3);C3-N2-B,122.5(3); C4-N2-B,129.9(3); N1-B-N2,106.8(3); N1-B-F5,108.1(4); N2-B-F6,107.9(4);F5-B-F6,110.1(4).
[65] Goze, C.; Ulrich, G.; Ziessel, R. Org. Lett.,2006,8,4445.
[66]11的部分键角(°)键长(): N1-B,1.561(3); N2-B,1.553(4); C5-B,1.592(3); C6-B,1.595(4);N1-B-N2,106.3°; N1-B-C5,109.3°. N2-B-C6,109.7°; C5-B-C6,111.5°.
[67] Sens, R.; Drexhage, K. H. J. Lumin.,1981,24,709.
[68](a) Lu, H.; Shimizu, S.; Mack, J.; Shen, Z.; Kobayashi, N. Chem. Asian J.,2011,6,1026.(b) Gresser,R.; Hummert, M.; Hartmann, H.; Leo, K.; Riede, M. Chem. Eur. J.,2011,17,2939.
[69] Song, L.; Trogler, W. C. Angew. Chem., Int. Ed.1992,31,770.
[70](a) Yang, L.; Simionescu, R.; Lough, A.; Yan, H. Dyes Pigm.,2011,91,264.(b) Crawford, S. M.;Thompson, A. Org Lett.,2010,12,14
[2](a)Harriman, A.; Mallon, L. J.; Goeb, S.; Ziessel, R. Chem. Phys.,2007,9,5199.(b) Yamada, K.;Nomura, Y.; Citterio, D.; Iwasawa, N.; Suzuki, K. J. Am. Chem. Soc.,2005,127,6956.(c)Wang,J.;Qian, X. Org. Lett.,2006,8,3721.(d)Hudnall, T.W.;Gabbai,F. P. Chem. Commun.,2008,4596.(e)Domaille, D.W.; Zeng, L.; Chang,C. J. J. Am. Chem. Soc.,2010,132,1194.(f) Atilgan, E.; Ozdemir,E.;Akkaya, E. U. Org. Lett.,2010,12,4792.
[3] Patterson, G. H. Science,2003,300,87.
[4] Khodjakov, A. Science,2003,300,91.
[5]陈小利，李翠红，宋庆宝.浙江化工，2010,41,18.
[6] Qin, W.; Barush, M.; Stefan, A.; Auweraer, M. V.; Boens, N. Chem. Phys.,2005,6,2343.
[7] Cox, R. D.; Vernon, D. I.; Griffiths, J.; Brown, S. Photochem. Photobiol.,2002,75,392.
[8] Coskun, A.; Akkaya, E. U. Tetra. Lett.,2004,45,4947.
[9] Wagner, R. W.; Lindsey, J. S. Pure.Appl. Chem.,1996,68,1373.
[10] Schulman S G． Fluorescence and Phosphorescence Spectroscopy. Physicochemical Principles andPractic．New York：oxford,1977．
[11]陈国珍，黄贤智，许金钩．荧光分析法(第二版)．北京：科学出版社，1900．
[12]张华山，王红，赵媛嫒．分子探针与检测试剂．北京：科学出版社，2002．
[13]西川秦治，平木敬三．分析化学译刊，1987．
[14] Haugland R P．Handbook of Fluorescent Probes and Research Chemicals．6th ed．1996．
[15] Strekowski L, Lee H, Lin S. J. Org. Chem.,2000,65(22)：7703-7705.
[16] Zhang Z, Achilefu S. Org. Lett.,2004,6,2067-2070.
[17] Mishra, Behera R K，Behera P K et a1. A Review. Chem. Rev.,2000，100(6)：1973-2012.
[18] Wu Y，Peng X，Guo B et a1. Org. Biomol. Chem.,2005,3,1387-1392.
[19] Takakusa B，Kikuchi K, Urano Y et a1. J. Am. Chem. Soc.,2002,124,1653-1657.
[20] Rogers, M. A. T. J. Chem. Soc.,1943,590.
[21] Zhang Y, Yang R H, Liu Fet a1. Anal. Chem.,2006,76,7336-7345.
[22] Gawronski J, Gawronska K, Skowronek P et a1. J. Org. Chem.,1999,64,234-241.
[23] Woodroofe C C, Lippard S J. J. Am. Chem. Soc.,2003,125,11458-11459.
[24] Karolin J, Johansson L B, Strandberg L et a1. J. Am. Chem. Soc.,1994,116,7801-7806.
[25] Meltola N J, Soini A E, Hanninen P E. Journal of Fluorescence,2004,14,129-138．
[26]刘欣，王红，张华山.分析科学学报，2001，17，346.
[27] Karolin, J.; Johansson, L. B.; Strandberg, L. J. Am. Chem. Soc.,1994,116,7801.
[28] McDonnell, S. O,; Hall, M. J.; Allen, L. T. J. Am. Chem. Soc.,2005,127,16360.
[29] Gallagher, W. M.; Allen, L. T.; O'Shea, C. J. Cancer,2005,92,1702.
[30] O'Shea, D.; Killoran, J.; Gallagher, W. US,7220732[P].2007.
[31] Armin Burghart, Heejin Kim, Kevin Burgess et a1. J. Org. Chem.,1999,64,7813-7819.
[32] Weili Zhao, Erick Carreira. Angew. Chem. Int. Ed.,2005,117,1705-1707.
[33] Treibs A, Kreuzer F H. Angew. Chem. Int. Ed.,1968,718,208-216.
[34] Worries H J, Koek J H. Recl. Tray. Chim. Pays-Bas.1985,104,288-291.
[35] Haugland R P, Kang H C. US4774339.1988.
[36] Kang R C. WO93/09185.1993.
[37] Haugland R P, Kang H C. US5433896.1995.
[38] Zhao W, Carreira E M. Angew. Chem. Int. Ed.,2005,44,1677-1679.
[39] Ulrich G, Goze C, Guardigli M et a1. Angew. Chem. Int. Ed.,2005,44,3694.
[40] Kim H, Burghart A,Welch M B et a1., Chem. Comun.,1999,1889-1890.
[41] Cben J, Burghart A, Kovacs A et a1. J. Org. Chem.,2000,65,2900-2906.
[42] Chen J, Burghart A, Wan C. Tetrahedron Letters,2000,41,2303-2307.
[43] Chen J, Reibenspies J, Derecskei-Kovacs et a1. Chem. Commun.,1999,2501-2502.
[44] Loudet A,Bandichhor R,Burgess K.et.al. Org.Lett.,2008,10,4771-4774
[45] Palma A, Tasior M, Frimansson D.O.et.al. Org.Lett.,2009,11,3638-3641
[46] Xin-Dong Jiang, Jian Zhang,Taniyuki Furuyama,and Weili Zhao. Org.Lett.,2012,14,248-251
[47] Chouaib Tahtaoui, Marcel Hibert.et.al.J. Org. Chem.,2007,72:269-272.
[48] Travis Lundrigan, Alison Thompson.et.al. Chem. Commun.,2012,48,1003-1005.
[49] Christine Goze, Gilles Ulrich. et.al. J. Am. Chem. Soc.,2006,128,10231
[50] Barthram, A. M.; Cleary, R. L.; Kowallick, R.; Ward, M. D. Chem. Commun.,1998,2695.
[51](a) Ntziachristos, V.; Ripoll, J.; Weissleder, R. Opt. Lett.,2002,27,333.(b) Sowell, J.; Strekowski, L.;Patonay, G. J. Biomed. Opt.,2002,7,571.
[52](a) Haugland, R. P.; Spence, M. T. Z.; Johnson, I. D.; Basey, A. The Handbook: A Guide toFluorescent Probes and Labeling Technologies,10th ed.; Molecular Probes: Eugene, OR,2005.(b)Karolin, J.; Johansson, L. B.-A.; Strandberg, L.; Ny, T. J. Am. Chem. Soc.,1994,116,7801.(c) Wan,C.-W.; Burghart, A.; Chen, J.; Bergstrom, F.; Johanson, L. B.-A.; Wolford, M. F.; Kim, T. G.; Topp,M. R.; Hochstrasser, R. M.; Burgess, K. Chem. Eur. J.,2003,9,4430.
[53] Chen, J.; Burghart, A.; Derecskei-Kovacs, A.; Burgess, K. J. Org. Chem.2000,65,2900.
[54](a) Umezawa, K.; Nakamura, Y.; Makino, H.; Citterio, D.; Suzuki, K. J. Am. Chem. Soc.,2008,130,1550.(b) Umezawa, K.; Matsui, A.; Nakamura, Y.; Citterio, D.; Suzuki, K. Chem. Eur. J.,2009,15,1096.(c) Awuah, S. G.; Polreis, J.; Biradar, V.; You, Y. Org. Lett.,2011,13,3884.
[55](a) Killoran, J.; Allen, L.; Gallagher, J.; Gallagher, W.; O’Shea, D. F. Chem. Commun.,2002,1862.(b)Gorman, A.; Killoran, J.; O’Shea, C.; Kenna, T.; Gallagher, W. M.; O’Shea, D. F. J. Am. Chem. Soc.,2004,126,10619.(c) McDonnell, S. O.; Hall, M. J.; Allen, L. T.; Byrne, A.; Gallagher, W. M.;O’Shea, D. F. J. Am. Chem. Soc.,2005,127,16360.(d) Killoran, J.; O’Shea, D. F. Chem. Commun.,2006,1503.
[56] Goze, C.; Ulrich, G.; Ziessel, R. J. Org. Chem.,2007,72,313.
[57](a) Goze, C.; Ulrich, G.; Ziessel, R. Org. Lett.,2006,8,4445.(b) Ulrich, G.; Goze, C.; Goeb, S.;Retailleau, P.; Ziessel, R. New J. Chem.,2006,30,9822.(c) Goeb, S.; Ziessel, R. Org. Lett.,2007,9,737.(d) Bonardi, L.; Ulrich, G.; Ziessel, R. Org. Lett.,2008,10,2183.(e) Ulrich, G.; Goze, C.;Guardigli, M.; Roda, A.; Ziessel, R. Angew. Chem., Int. Ed.2005,44,3694.
[58] Palma, A.; Tasior, M.; Frimannsson, D. O.; Vu, T. T.; Méallet-Renault, R.; O’Shea, D. F. Org. Lett.,2009,11,3638.
[59] Jiang, X.-D.; Zhang, J.; Fukuyama, T.; Zhao, W. Org. Lett.,2012,14,248.
[60](a) Loudet, A.; Bandichhor, R.; Burgess, K.; Palma, A.; McDonnell, S. O.; Hall, M. J.; O’Shea, D. F.Org. Lett.,2008,10,4771.(b) Yakubovskyi, V. P.; Shandura, M. P.; Kovtun, Y. P. Synth. Commun.,2010,40,944.
[61](a) Li, Y.; Patrick, B. O.; Dolphin, D. J. Org. Chem.,2009,74,5237.(b) Descalzo, A. B.; Rurack, K.Chem.-Eur. J.,2009,15,3173.(c) Kubo, Y.; Yoshida, K.; Adachi, M.; Nakamura, S.; Maeda, S. J. Am.Chem. Soc.,1991,113,2868.(d) Barthram, A. M.; Cleary, R. L.; Kowallick, R.; Ward, M. D. Chem.Commun.,1998,2695.(e) Li, H.; Nguyen, N.; Fronczek, F. R.; Vicente, M. G. H. Tetrahedron,2009,65,3357.
[62](a) Jiang, X.-D.; Zhang, J.; Shao, X.; Zhao, W. Org. Biomol. Chem.,2012,10,1966.(b) Zhao, W.;Carreira, E. M. Angew. Chem., Int. Ed.2005,44,1677.(c) Zhao, W.; Carreira, E. M. Chem. Eur. J.,2006,12,7254.
[63] Goze, C.; Ulrich, G.; Mallon, L. J.; Allen, B. D.; Harriman, A.; Ziessel, R. J. Am. Chem. Soc.,2006,128,10231.
[64]9和10的部分键角()和键长(°): N1-C1,1.403(3); N1-C2,1.352(3); N2-C3,1.407(3); N2-C4,1.353(3); N1-B,1.586(3); N2-B,1.580(3); C5-B,1.636(3); C6-B,1.616(3); C1-N1-C2,107.8(2);C1-N1-B,122.7(2); C2-N1-B,128.7(2); C3-N2-C4,107.6(2); C3-N2-B,122.7(2); C4-N2-B,127.7(2);N1-B-N2,104.6(2); N1-B-C5,108.8(2); N2-B-C6,110.9(2); C5-B-C6,115.0(2).: N1-C1,1.409(4);N1-C2,1.360(4); N2-C3,1.395(4); N2-C4,1.360(4); N1-B,1.562(5); N2-B,1.561(5); F5-B,1.365(5);F6-B,1.377(5); C1-N1-C2,106.9(3); C1-N1-B,121.5(3); C2-N1-B,130.9(3); C3-N2-C4,107.0(3);C3-N2-B,122.5(3); C4-N2-B,129.9(3); N1-B-N2,106.8(3); N1-B-F5,108.1(4); N2-B-F6,107.9(4);F5-B-F6,110.1(4).
[65] Goze, C.; Ulrich, G.; Ziessel, R. Org. Lett.,2006,8,4445.
[66]11的部分键角(°)键长(): N1-B,1.561(3); N2-B,1.553(4); C5-B,1.592(3); C6-B,1.595(4);N1-B-N2,106.3°; N1-B-C5,109.3°. N2-B-C6,109.7°; C5-B-C6,111.5°.
[67] Sens, R.; Drexhage, K. H. J. Lumin.,1981,24,709.
[68](a) Lu, H.; Shimizu, S.; Mack, J.; Shen, Z.; Kobayashi, N. Chem. Asian J.,2011,6,1026.(b) Gresser,R.; Hummert, M.; Hartmann, H.; Leo, K.; Riede, M. Chem. Eur. J.,2011,17,2939.
[69] Song, L.; Trogler, W. C. Angew. Chem., Int. Ed.1992,31,770.
[70](a) Yang, L.; Simionescu, R.; Lough, A.; Yan, H. Dyes Pigm.,2011,91,264.(b) Crawford, S. M.;Thompson, A. Org Lett.,2010,12,14