基于9-亚环庚三烯基芴类荧光传感器的合成及性能研究
|
摘要
本论文主要研究了9-亚环庚三烯基芴类荧光传感器的合成及对金属离子的响应。
利用Sonagoshira偶联反应，合成了具有氮杂冠醚结构的9-亚环庚三烯基芴类的化合物，并通过氢谱、碳谱、质谱对合成的分子结构进行了表征。同时，我们利用紫外可见吸收和稳态荧光光谱仪，考察了这些化合物的光物理现象，发现化合物存在从离子传感部分到荧光发射部分的电荷转移(CT)。
通过研究这些化合物对金属离子的响应，我们发现：在乙腈溶剂中，N,N-二乙二醇乙醚取代的9-亚环庚三烯基芴(7)对三价铁离子和二价铜离子有着灵敏的荧光响应以及很好的选择性(对Na~+；Fe~(2+)；Ag~+；Zn~(2+)；Co~(2+)；Cd~(2+)；Ni~(2+)；Mg~(2+)；Ca~(2+)；Hg~(2+)；Mn~(2+)；K~+；Ba~(2+)；Li~+；Pb~(2+)；Cs~+；Cr~(3+)和Sm~(3+)无响应)，表现为荧光淬灭；而通过N,N-二β-羟基乙基取代的9-亚环庚三烯基芴(8)和三价铁离子在甲醇中的荧光增强、8和二价铜离子在乙腈中的荧光增强现象，我们可以实现对三价铁离子和二价铜离子的识别。
进一步研究表明，荧光增强是由于溶液中存在9-亚环庚三烯基芴和金属离子的纳米聚集体，由此产生聚集体荧光增强效应。我们分别通过透射电镜和动态光散射证明了纳米聚集体的存在，并就聚集体的形成机理进行了探讨。
In this dissertation, 9-(cycloheptatrienylidene)fluorene derivatives function as fluorescent chemosensor for metal ions were designed and discussed.
9-(Cycloheptatrienylidene)fluorene derivatives with heterocrown ether structure have been prepared by well known Sonagoshira coupling reaction, and their structures were characterized by ~1H NMR ~(13)C NMR and MS. Their optical properties have been measured by UV-vis spectropHotometer and spectrofluorometer, which show the intramolecular charge transfer.
2,7-Bis(2-(4-(di(2-(2-ethoxyethoxy)ethyl)amino)pHenyl)ethynyl)-9-(cyclohepta trienylidene)fluorine (7) exhibits high sensitivity and selectivity for Cu~(2+) or Fe~(3+) (no response to Na~+; Fe~(2+); Ag~+; Zn~(2+); Co~(2+); Cd~(2+); Ni~(2+); Mg~(2+); Ca~(2+); Hg~(2+); Mn~(2+); K~+; Ba~(2+); Li~+; Pb~(2+); Cs~+; Cr~(3+) and Sm~(3+)), and displayed quenched emission when either Cu~(2+) or Fe~(3+) was added into its acetonitrile solution. However, 2, 7-bis(2-(4-(di(2-hydroxyethyl)amino)pHenyl)ethynyl)-9-(cycloheptatrienylidene)flu orine (8) could successfully identify Fe~(3+) or Cu~(2+) by enhanced emission with addition of Fe~(3+) in its methanol or with addition of Cu~(2+) in its acetonitrile.
With the futher study, we find that emission enhancement was ascribed to nano-aggregates formation, which was induced by supramolecular self-assembly between non-benzenoid hydrocarbons and metal ions through intermolecular electrostatic force in organic solvent. Both transmission electron microscope (TEM) and dynamic light scattering (DLS) proved the existence of nano aggregates.
利用Sonagoshira偶联反应，合成了具有氮杂冠醚结构的9-亚环庚三烯基芴类的化合物，并通过氢谱、碳谱、质谱对合成的分子结构进行了表征。同时，我们利用紫外可见吸收和稳态荧光光谱仪，考察了这些化合物的光物理现象，发现化合物存在从离子传感部分到荧光发射部分的电荷转移(CT)。
通过研究这些化合物对金属离子的响应，我们发现：在乙腈溶剂中，N,N-二乙二醇乙醚取代的9-亚环庚三烯基芴(7)对三价铁离子和二价铜离子有着灵敏的荧光响应以及很好的选择性(对Na~+；Fe~(2+)；Ag~+；Zn~(2+)；Co~(2+)；Cd~(2+)；Ni~(2+)；Mg~(2+)；Ca~(2+)；Hg~(2+)；Mn~(2+)；K~+；Ba~(2+)；Li~+；Pb~(2+)；Cs~+；Cr~(3+)和Sm~(3+)无响应)，表现为荧光淬灭；而通过N,N-二β-羟基乙基取代的9-亚环庚三烯基芴(8)和三价铁离子在甲醇中的荧光增强、8和二价铜离子在乙腈中的荧光增强现象，我们可以实现对三价铁离子和二价铜离子的识别。
进一步研究表明，荧光增强是由于溶液中存在9-亚环庚三烯基芴和金属离子的纳米聚集体，由此产生聚集体荧光增强效应。我们分别通过透射电镜和动态光散射证明了纳米聚集体的存在，并就聚集体的形成机理进行了探讨。
In this dissertation, 9-(cycloheptatrienylidene)fluorene derivatives function as fluorescent chemosensor for metal ions were designed and discussed.
9-(Cycloheptatrienylidene)fluorene derivatives with heterocrown ether structure have been prepared by well known Sonagoshira coupling reaction, and their structures were characterized by ~1H NMR ~(13)C NMR and MS. Their optical properties have been measured by UV-vis spectropHotometer and spectrofluorometer, which show the intramolecular charge transfer.
2,7-Bis(2-(4-(di(2-(2-ethoxyethoxy)ethyl)amino)pHenyl)ethynyl)-9-(cyclohepta trienylidene)fluorine (7) exhibits high sensitivity and selectivity for Cu~(2+) or Fe~(3+) (no response to Na~+; Fe~(2+); Ag~+; Zn~(2+); Co~(2+); Cd~(2+); Ni~(2+); Mg~(2+); Ca~(2+); Hg~(2+); Mn~(2+); K~+; Ba~(2+); Li~+; Pb~(2+); Cs~+; Cr~(3+) and Sm~(3+)), and displayed quenched emission when either Cu~(2+) or Fe~(3+) was added into its acetonitrile solution. However, 2, 7-bis(2-(4-(di(2-hydroxyethyl)amino)pHenyl)ethynyl)-9-(cycloheptatrienylidene)flu orine (8) could successfully identify Fe~(3+) or Cu~(2+) by enhanced emission with addition of Fe~(3+) in its methanol or with addition of Cu~(2+) in its acetonitrile.
With the futher study, we find that emission enhancement was ascribed to nano-aggregates formation, which was induced by supramolecular self-assembly between non-benzenoid hydrocarbons and metal ions through intermolecular electrostatic force in organic solvent. Both transmission electron microscope (TEM) and dynamic light scattering (DLS) proved the existence of nano aggregates.
引文
[1] Hulanicki, A.; Glab, S.; Ingman, F. Chemical Sensor 2004, 4, 14.
[2] Michael, M.; Knut R. New J. Chem., 2000, 24, 677.
[3] 丁立平：高莉宁；房喻：科技进展 2003，25，280．
[4] 王煜；晋卫军 化学进展2003，15，179．
[5] Kunt, R.; Ute, R.G. Chem. Soc. Rev. 2002, 31, 116.
[6] Pallavicini, P.; Valeria, A.; Massera, C.; Munduma, E.; Tagliettia, A. Chem Comm 2002, 10, 2453.
[7] de Silva, A. P.; Dixon, I. M.; Gunaratne, H. Q. N.; Gunnlaugsson, T.; Maxwell, P. R. S.; Rice, T. E. J. Am. Chem. Soc. 1999, 121, 1393.
[8] de Silva, A. P.; Gunaratne, H. Q. N. J. Chem. Soc. Chem. Commun. 1990, 186.
[9] de Silva, A. P.; Gunaratne, H. Q. N.; Maguire, G. E. M. J. Chem. Soc. Chem. Commun. 1994, 11213.
[10] Kubo, K.; Ishige, R.; Kubo, J.; et al. Talanta. 1999, 48, 181.
[11] Meadows, E. S.; de Wall, S. L.; Barbour, L. J.; et al. Chem. Commun. 1999, 1555.
[12] Kubo, K.; Yarnamoto, E.; Sakurai, T. Heterocycles. 1998, 48, 2133.
[13] Kubo, K.; Ishige, R.; Sakurai, T. Heterocycles. 1998, 48, 347.
[14] Wang, W. L.; Xu, J. W.; Lai, Y. H. J. Polym. Sci., PartA: Polym. Chem. 2006, 44, 4154.
[15] De Santis, G.; Fabrizzi, L.; Licchelli, M.; et al. lnorg. Chem. 1995, 34, 3581.
[16] Fabrizzi, L.; Licchelli, M.; Pallavicini, P. Acc. Chem. Res. 1999, 32, 846.
[17] Fabbrizzi, L.; Francesco, G.; Pallavicini, P.; Parodi, L. New J. Chem. 1998, 1403
[18] Métivier, R.; Leray, I.; Bernard, V. Chem. Commun. 2003, 996.
[19] Higuchi, Y.; Narita, M.; Niimi, T.; Ogawa, N.; Hamada, F.; Kumagai, H.; Iki, N.; Miyano S.; Kabuto, C. Tetrahedron, 2000, 56, 4659.
[20] Elizabeth, M.; StepHen J.; Lippard. J. Am. Chem. Soc 2003, 125, 14270.
[21] Prodi, L.; Montalti, M.; Zaccheroni, N.;et al. Tetrahedron Lett. 2001, 42, 2941.
[22] Coskun, A.; Baytekin, B. T.; Akkaya, E. U. Tetrahedron Lett. 2003, 4, 5649.
[23] Li, Z.; Evan, W. M.; Arnd, P.; Ehud Y. I.; ChristopHer, J. C. J. Am. Chem. Soc. 2006, 128, 10.
[24] Yu, X.; Tong, A. J. Org. Lett. 2006, 8, 1549.
[25] Liu, H.; Wang, S.; Luo, Y.; Tang, W.; Yu, G.; Li, L.; Chen, C; Liu,Y.; Xi, F. J. Mater. Chem. 2001,11, 3063.
[26] Xia, W. S.; Schme, M. R. H.; Li, C. J.; Magne, J. T.; Luo, C. P.; Glidi, D. M. J. PHys. Chem. B. 2002, 106, 833.
[27] Xu, Z. C.; Xiao, Y.; Qian, X. H.; Cui, J.; Cui, D. W. Org. Lett. 2005, 7, 889.
[28] Xu, Z.; Qian, X.; Cui, J. Org. Lett. 2005, 7, 3029.
[29] Wang, J. B.; Qian, X.H.; Cui, J. J. Org. Chem. 2006, 71, 4308.
[30] Xu, Z. C; Qian, X. H.; Cui, J.; Zhang, R. Tetrahedron 2006, 62, 10117.
[31] Descalzo, A. B.; Martinez-Manez, R.; Radeglia, R.; Rurack, K.; Soto, J. J. Am. Chem. Soc. 2003, 125, 3418.
[32] Xia, W. S.; Schmem, R. H.; Li, C. J.;Magne, J. T.; Luo, C. P. J. PHys. Chem. B. 2002, 106, 833
[33] Sancenon F.; Matinez-Manez, R. Sato, J. Tetrahedron Lett. 2003, 5, 4065.
[34] Karolin, J.; Johansson, L. B.; Strandberg, L.; et al. J. Am. Chem. Soc. 1994, 116, 7801.
[35] Rurack, K.; Kollmannsberger, M.; Resch-Genger, U.; Daub, J. J. Am. Chem. Soc. 2000,122, 968.
[36] Yoon, S.; Albers, A. E.; Wong, A. P.; Chang, C. J. J. Am. Chem. Soc. 2005,127, 16030.
[37] Krauss, R.; Weinig, H. G.; Seydack, M. et al. Angew. Chem. Int. Ed. 2000, 39, 1835.
[38] Licchelli, M.; Biroli, A. O.; Poggi, A. Org. Lett. 2006, 8, 915.
[39] Marquis, D.; Desvergne, J. P.; Bouas, L. H. J. Org. Chem. 1995, 60, 7984
[40] Fages, F.; Desvergne, J. P.; Bouas, L. H. J. Org. Chem. 1994, 59, 5264.
[41] Arunkumar, E.; Ajayaghosh, A.; Daub, J. J. Am. Chem. Soc. 2005,127, 3156.
[42] Yamaguchi, S.; Akiyama, S.; Tarmao, K. J. Am. Chem. Soc. 2000,122, 6793.
[43] Yasuhiro, S.; Yasufumi, T.; Takayuki, H. Org. Lett. 2006, 8, 3841.
[44] Benjamin, S.; Nameer A.; Dermot D. J. Am. Chem. Soc. 2006,128, 8607.
[1] Prinzbach, H.; Seip, D.; Knothe, L.; Faisst, W. Justus Liebigs Ann. Chem. 1966, 698, 34.
[2] Ostrowski, S.; Makosza, M. Liebigs Ann. Chem. 1989, 95.
[3] Minabe, M.; Tomiyama, T.; Nozawa, T.; Noguchi, M.; Nakao, A.; Oba, T.; Kimura, T. Bull. Chem. Soc. Jpn. 2001, 74, 1093.
[4] Wang, Z. X.; Li, W.; Lu, P. Sensors and Actuators B. 2004.99. 264
[5] Wang, Z. X.; Xing, Y. J.; Shao, H. X.; Lu, P.; William, P.W. Org. Lett. 2005, 7, 87.
[6] Wang, Z. X.; Zheng, G. R.; Lu, P. Org. Lett. 2005, 7, 3669.
[7] Amendola, V.; Fabbrizzi, L.; Mangano, C.; Miller, H.; Pallavicini, P.; Perotti, A.; Taglietti, A. Angew. Chem. Int. Ed. 2002, 41, 2533
[8] Zheng, G. R.; Wang Z. X.; Tang, L.; Lu, P.; Weber, W. P.; Sensors and Actuators B 2007, 122, 389-394.
[9] Liu, J. M.; Zheng, Q. Y.; Yang, J. L.; Chen, C. F.; Huang, Z. T. Tetrahedron Letters. 2002, 43, 9209.
[10] Luo, J.; Xie, Z.; Larn, J. W. Y.; Cheng, L.; Chen, H.; Qiu, C.; Kwok, H. S.; Zhan, X.; Liu, Y.; Zhu, D.; Tang, B. Z. Chem. Commun. 2001, 1740.
[1] Conrow, K. Org. Syn. 1963, 5, 1138.
[2] Minabe, M.; Tomiyama, T.; Nozawa, T.; Noguchi, M.; Nakao, A.; Oba, T.; Kimura, T. Bull. Chem. Soc. Jpn. 2001, 74, 1093.
[3] Huang, J. H.; Wen, W. H.; Sun, Y. Y.; Chou, P. T.; Fang, J. M. J. Org. Chem. 2005, 70, 5827.
[2] Michael, M.; Knut R. New J. Chem., 2000, 24, 677.
[3] 丁立平：高莉宁；房喻：科技进展 2003，25，280．
[4] 王煜；晋卫军 化学进展2003，15，179．
[5] Kunt, R.; Ute, R.G. Chem. Soc. Rev. 2002, 31, 116.
[6] Pallavicini, P.; Valeria, A.; Massera, C.; Munduma, E.; Tagliettia, A. Chem Comm 2002, 10, 2453.
[7] de Silva, A. P.; Dixon, I. M.; Gunaratne, H. Q. N.; Gunnlaugsson, T.; Maxwell, P. R. S.; Rice, T. E. J. Am. Chem. Soc. 1999, 121, 1393.
[8] de Silva, A. P.; Gunaratne, H. Q. N. J. Chem. Soc. Chem. Commun. 1990, 186.
[9] de Silva, A. P.; Gunaratne, H. Q. N.; Maguire, G. E. M. J. Chem. Soc. Chem. Commun. 1994, 11213.
[10] Kubo, K.; Ishige, R.; Kubo, J.; et al. Talanta. 1999, 48, 181.
[11] Meadows, E. S.; de Wall, S. L.; Barbour, L. J.; et al. Chem. Commun. 1999, 1555.
[12] Kubo, K.; Yarnamoto, E.; Sakurai, T. Heterocycles. 1998, 48, 2133.
[13] Kubo, K.; Ishige, R.; Sakurai, T. Heterocycles. 1998, 48, 347.
[14] Wang, W. L.; Xu, J. W.; Lai, Y. H. J. Polym. Sci., PartA: Polym. Chem. 2006, 44, 4154.
[15] De Santis, G.; Fabrizzi, L.; Licchelli, M.; et al. lnorg. Chem. 1995, 34, 3581.
[16] Fabrizzi, L.; Licchelli, M.; Pallavicini, P. Acc. Chem. Res. 1999, 32, 846.
[17] Fabbrizzi, L.; Francesco, G.; Pallavicini, P.; Parodi, L. New J. Chem. 1998, 1403
[18] Métivier, R.; Leray, I.; Bernard, V. Chem. Commun. 2003, 996.
[19] Higuchi, Y.; Narita, M.; Niimi, T.; Ogawa, N.; Hamada, F.; Kumagai, H.; Iki, N.; Miyano S.; Kabuto, C. Tetrahedron, 2000, 56, 4659.
[20] Elizabeth, M.; StepHen J.; Lippard. J. Am. Chem. Soc 2003, 125, 14270.
[21] Prodi, L.; Montalti, M.; Zaccheroni, N.;et al. Tetrahedron Lett. 2001, 42, 2941.
[22] Coskun, A.; Baytekin, B. T.; Akkaya, E. U. Tetrahedron Lett. 2003, 4, 5649.
[23] Li, Z.; Evan, W. M.; Arnd, P.; Ehud Y. I.; ChristopHer, J. C. J. Am. Chem. Soc. 2006, 128, 10.
[24] Yu, X.; Tong, A. J. Org. Lett. 2006, 8, 1549.
[25] Liu, H.; Wang, S.; Luo, Y.; Tang, W.; Yu, G.; Li, L.; Chen, C; Liu,Y.; Xi, F. J. Mater. Chem. 2001,11, 3063.
[26] Xia, W. S.; Schme, M. R. H.; Li, C. J.; Magne, J. T.; Luo, C. P.; Glidi, D. M. J. PHys. Chem. B. 2002, 106, 833.
[27] Xu, Z. C.; Xiao, Y.; Qian, X. H.; Cui, J.; Cui, D. W. Org. Lett. 2005, 7, 889.
[28] Xu, Z.; Qian, X.; Cui, J. Org. Lett. 2005, 7, 3029.
[29] Wang, J. B.; Qian, X.H.; Cui, J. J. Org. Chem. 2006, 71, 4308.
[30] Xu, Z. C; Qian, X. H.; Cui, J.; Zhang, R. Tetrahedron 2006, 62, 10117.
[31] Descalzo, A. B.; Martinez-Manez, R.; Radeglia, R.; Rurack, K.; Soto, J. J. Am. Chem. Soc. 2003, 125, 3418.
[32] Xia, W. S.; Schmem, R. H.; Li, C. J.;Magne, J. T.; Luo, C. P. J. PHys. Chem. B. 2002, 106, 833
[33] Sancenon F.; Matinez-Manez, R. Sato, J. Tetrahedron Lett. 2003, 5, 4065.
[34] Karolin, J.; Johansson, L. B.; Strandberg, L.; et al. J. Am. Chem. Soc. 1994, 116, 7801.
[35] Rurack, K.; Kollmannsberger, M.; Resch-Genger, U.; Daub, J. J. Am. Chem. Soc. 2000,122, 968.
[36] Yoon, S.; Albers, A. E.; Wong, A. P.; Chang, C. J. J. Am. Chem. Soc. 2005,127, 16030.
[37] Krauss, R.; Weinig, H. G.; Seydack, M. et al. Angew. Chem. Int. Ed. 2000, 39, 1835.
[38] Licchelli, M.; Biroli, A. O.; Poggi, A. Org. Lett. 2006, 8, 915.
[39] Marquis, D.; Desvergne, J. P.; Bouas, L. H. J. Org. Chem. 1995, 60, 7984
[40] Fages, F.; Desvergne, J. P.; Bouas, L. H. J. Org. Chem. 1994, 59, 5264.
[41] Arunkumar, E.; Ajayaghosh, A.; Daub, J. J. Am. Chem. Soc. 2005,127, 3156.
[42] Yamaguchi, S.; Akiyama, S.; Tarmao, K. J. Am. Chem. Soc. 2000,122, 6793.
[43] Yasuhiro, S.; Yasufumi, T.; Takayuki, H. Org. Lett. 2006, 8, 3841.
[44] Benjamin, S.; Nameer A.; Dermot D. J. Am. Chem. Soc. 2006,128, 8607.
[1] Prinzbach, H.; Seip, D.; Knothe, L.; Faisst, W. Justus Liebigs Ann. Chem. 1966, 698, 34.
[2] Ostrowski, S.; Makosza, M. Liebigs Ann. Chem. 1989, 95.
[3] Minabe, M.; Tomiyama, T.; Nozawa, T.; Noguchi, M.; Nakao, A.; Oba, T.; Kimura, T. Bull. Chem. Soc. Jpn. 2001, 74, 1093.
[4] Wang, Z. X.; Li, W.; Lu, P. Sensors and Actuators B. 2004.99. 264
[5] Wang, Z. X.; Xing, Y. J.; Shao, H. X.; Lu, P.; William, P.W. Org. Lett. 2005, 7, 87.
[6] Wang, Z. X.; Zheng, G. R.; Lu, P. Org. Lett. 2005, 7, 3669.
[7] Amendola, V.; Fabbrizzi, L.; Mangano, C.; Miller, H.; Pallavicini, P.; Perotti, A.; Taglietti, A. Angew. Chem. Int. Ed. 2002, 41, 2533
[8] Zheng, G. R.; Wang Z. X.; Tang, L.; Lu, P.; Weber, W. P.; Sensors and Actuators B 2007, 122, 389-394.
[9] Liu, J. M.; Zheng, Q. Y.; Yang, J. L.; Chen, C. F.; Huang, Z. T. Tetrahedron Letters. 2002, 43, 9209.
[10] Luo, J.; Xie, Z.; Larn, J. W. Y.; Cheng, L.; Chen, H.; Qiu, C.; Kwok, H. S.; Zhan, X.; Liu, Y.; Zhu, D.; Tang, B. Z. Chem. Commun. 2001, 1740.
[1] Conrow, K. Org. Syn. 1963, 5, 1138.
[2] Minabe, M.; Tomiyama, T.; Nozawa, T.; Noguchi, M.; Nakao, A.; Oba, T.; Kimura, T. Bull. Chem. Soc. Jpn. 2001, 74, 1093.
[3] Huang, J. H.; Wen, W. H.; Sun, Y. Y.; Chou, P. T.; Fang, J. M. J. Org. Chem. 2005, 70, 5827.