含磷酰杂菲侧基的苯乙烯衍生物聚集诱导发光特性及其在过渡金属离子检测中的应用

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (8): 1656.

含磷酰杂菲侧基的苯乙烯衍生物聚集诱导发光特性及其在过渡金属离子检测中的应用

申进波¹, 佟斌¹, 石建兵¹, 孙书¹, 冯霄¹, 支俊格², 董宇平¹

1. 北京理工大学材料学院,
2. 理学院, 北京 100081

收稿日期:2009-10-13 出版日期:2010-08-10 发布日期:2010-08-10
通讯作者: 董宇平, 男, 博士, 教授, 主要从事高分子合成化学和有机功能材料研究. E-mail: chdongyp@bit.edu.cn
基金资助:
国家自然科学基金(批准号: 20634020)资助.

Aggregation-Induced Emission Enhancement Properties of Phosphaphenanthrene-containing Styrene Derivant and Its Application of Detection to Transition Metal Ions

SHEN Jin-Bo1, TONG Bin1, SHI Jian-Bing1, SUN Shu1, FENG Xiao1, ZHI Jun-Ge2, DONG Yu-Ping1*

1. College of Materials,
2. College of Science, Beijing Institute of Technology, Beijing 100081, China

Received:2009-10-13 Online:2010-08-10 Published:2010-08-10
Contact: DONG Yu-Ping. E-mail: chdongyp@bit.edu.cn
Supported by:
国家自然科学基金(批准号: 20634020)资助.

摘要/Abstract

摘要： 以2-(6-氧化-6-氢-二苯基(c,e)<1,2>氧杂磷酰基)-1,4-二羟基苯(ODOPB) 为中心结构单元, 通过两步酯化反应, 在两侧分别引入4-戊氧基苯甲酰基和4-乙烯基苯甲酰基, 得到苯乙烯衍生物(MED).由于磷酰杂菲基团的大π共轭结构和极性共同作用, 使得形成聚集体后分子内转动受到限制, 降低了非辐射去活效率, 使 MED在达到一定聚集程度时, 荧光强度成倍增加, 呈现出聚集诱导发光增强(AIEE) 特性. 同时, Pt²⁺, Ru³⁺, Fe³⁺的加入对MED有显著的猝灭效果; 而Fe²⁺只是在形成聚集体过程中才有猝灭效果.

关键词: 磷酰杂菲, 聚集诱导发光增强, 分子内转动受限, 金属离子传感器

Abstract: Fluorescence of the organic light-emitting compounds are often quenched when the luminophors are fabricated into solid thin films, which have greatly limited their scope of practical applications. So, it is important to design and synthesize the novel organic luminophors with excellent light emission property in solid state. Phosphaphenanthrene-containing styrene derivant(MED) was synthesized by means of two-step esterification from 2-(6-oxide-6H-dibenz(c,e)<1,2>oxaphos-phorin-6-yl)dihydroxyphenylenes(ODOPB), 4-(pentyloxy)benzoic acid and 4-ethylenebenzoic acid, respectively. And then the compound was characterized by ¹H NMR, FTIR, mass spectra, UV-Vis and PL. When MED aggregates to a certain degree in mixture of water and acetonitrile, the fluorescence strength of MED proportionably increases, which shows obvious aggregation-induced emission enhancement(AIEE) property because the aggregation state of MED restricts the intramlecular rotation of phosphaphenanthrene group based on π-π stacking and polarity interaction between the molecules. Pt²⁺, Ru³⁺, Fe²⁺ and Fe³⁺ ions(1×10^-4 mol/L) can efficiently quench the emission intensity of MED(1×10^-5 mol/L) and higher than those by Pb²⁺, Zn²⁺, Cd²⁺, In²⁺, Co²⁺, Cu²⁺, Ni²⁺ and Ag⁺ ions. The quenching efficiency of Pt²⁺ and Ru³⁺ are the same when they are added into the mixture of water-acetonitrile(90/10, volume ratio) during or after the aggregation state formation of MED. Fe³⁺ shows the highest quenching efficiency to the PL of MAD during aggregation. If being added into the aggregated systems, Fe³⁺ has the same quenching ability to MED. Fe²⁺ only shows its quenching effect on MED during aggregation. This novel phenomenon may enable the molecule to find applications to discriminating chemosensors to detect the transition metal ions.

Key words: Phosphaphenanthrene, Aggregation-induced emission enhancement, Restriction of intramolecular rotation, Sensor to metal ion

TrendMD:

申进波, 佟斌, 石建兵, 孙书, 冯霄, 支俊格, 董宇平. 含磷酰杂菲侧基的苯乙烯衍生物聚集诱导发光特性及其在过渡金属离子检测中的应用. 高等学校化学学报, 2010, 31(8): 1656.

SHEN Jin-Bo, TONG Bin, SHI Jian-Bing, SUN Shu, FENG Xiao, ZHI Jun-Ge, .... Aggregation-Induced Emission Enhancement Properties of Phosphaphenanthrene-containing Styrene Derivant and Its Application of Detection to Transition Metal Ions. Chem. J. Chinese Universities, 2010, 31(8): 1656.

参考文献

[1]Xie Z. Q., Yang B., Li F., Cheng G., Liu L. L., Yang G. D., Xu H., Ye L., Hanif M., Liu S. Y., Ma D., Ma Y. G.. J. Am. Chem. Soc.[J], 2005, 127(41): 14152—14153 [2]SHI Min-Min(施敏敏), CHEN Hong-Zheng(陈红征), SUN Jing-Zhi(孙景志), YE Jian(叶坚), WANG Mang(汪茫). Chem. J. Chinese Universities(高等学校化学学报)[J], 2004, 25(3): 454—457 [3]SONG Xue-Liang(宋学良), JIN Jia-Ke(金佳科), DONG Hao-Yu(董浩宇), TANG Ben-Zhong(唐本忠), SUN Jing-Zhi(孙景志). Chem. J. Chinese Universities(高等学校化学学报)[J], 2006, 27(11): 2209—2212 [4]YING Lei(应磊) , CHEN Zhao(陈钊) , JIANG Jia-Xing(蒋加兴), GUAN Rong(管榕), YANG Wei(杨伟), CAO Yong(曹镛). Chem. J. Chinese Universities(高等学校化学学报)[J], 2009, 30(2): 403—407 [5]ZHANG Guang-Wei(张广维), FAN Qiu-Li(范曲立), HUANG Wei(黄维). Chem. J. Chinese Universities(高等学校化学学报)[J], 2009, 30(2): 413—416 [6]YANG Bing(杨兵) , MA Yu-Guang(马於光), SHEN Jia-Cong(沈家骢). Chem. J. Chinese Universities(高等学校化学学报)[J], 2008, 29(12): 2643—2658 [7]Huang J., Liu Q., Zou J. H., Zhu X. H., Li A. Y., Li J. W., Wu S., Peng J. B., Cao Y., Xia R. D., Bradley D. D. C., Roncali J.. Adv. Funct. Mater.[J], 2009, 19(18): 2978—2986 [8]Zhang W. M., Smith J., Hamilton R., Heeney M., Kirkpatrick J., Song K., Watkins S. E., Anthopoulos T., McCulloch I.. J. Am. Chem. Soc.[J], 2009, 131(31): 10814—10815 [9]Toal S. J., Jones K. A., Magde D., Trogler W. C.. J. Am. Chem. Soc.[J], 2005, 127(33): 11661—11665 [10]Luo J. D., Xie Z. L., Lam J. W. Y., Cheng L., Tang B. Z., Chen H. Y., Qiu C. F., Kwok H. S., Zhan X. W., Liu Y. Q., Zhu D. B.. Chem. Commun.[J], 2001, (18): 1740—1741 [11]Chen J. W., Law C. C. W., Lam J. W. Y., Dong Y. P., Lo S. M. F., Williams I. D., Zhu D. B., Tang B. Z.. Chem. Mater.[J], 2003, 15(7): 1535—1546 [12]Chen J. W., Xu B., Ouyang. X. Y., Tang B. Z., Cao Y.. J. Phys. Chem. A[J], 2004, 108(37): 7522—7526 [13]Dong Y. Q., Lam J. W. Y., Qin A. J., Li Z., Sun J. Z., Sung H. H. Y., Williams I. D. Tang B. Z.. Chem. Commun.[J], 2007, (1): 40—42 [14]Tong H., Dong Y. Q., Huβler M., Lam J. W. Y., Sung H. H. Y., Williams I. D., Sun J. Z., Tang B. Z.. Chem. Commun.[J], 2006, (10): 1133—1135 [15]An B. K., Kwon S. K., Jung S. D., Park S. Y.. J. Am. Chem. Soc.[J], 2002, 124(48): 14410—14415 [16]Wu C. C., Lin Y. T., Wong K. T., Chen Y. Y. C.. Adv. Mater.[J], 2004, 16(1): 61—65 [17]Li Z., Dong Y. Q., Tang Y. H., Hussler M., Tong H., Dong Y. P., Lam J. W. Y., Ren Y., Sung H. H. Y., Wong K. S., Gao P., Williams I. D., Kwok H. S., Tang B. Z.. J. Phys. Chem. B[J], 2005, 109(20): 10061—10066 [18]Bhongale C. J., Hsu C. S.. Angew. Chem. Int. Ed.[J], 2006, 45(9): 1404—1408 [19]Qin A. J., Jim C. K. W., Tang Y. H., Lam J. W. Y., Liu J. Z., Mahtab F., Gao P., Tang B. Z.. J. Phys. Chem. B[J], 2008, 112(31): 9281—9288 [20]Zhao Z. J., Wang Z. M., Lu P., Chan C. Y. K., Liu D. D., Lam J. W. Y., Sung H. H. Y., Williams I. D., Ma Y. G., Tang B. Z.. Angew. Chem. Int. Ed.[J] 2009, 48(41): 7608—7611 [21]Qian L. J., Tong B., Shen J. B., Shi J. B., Zhi J. G., Dong Y. Q., Yang F., Dong Y. P., Lam J. W. Y., Liu Y., Tang B, Z.. J. Phys. Chem. B[J], 2009, 113(27): 9098—9103 [22]QIAN Li-Jun(钱立军), TONG Bin(佟斌) , ZHI Jun-Ge(支俊格), YANG Fan(杨帆), SHEN Jin-Bo(申进波), SHI Jian-Bing(石建兵), DONG Yu-Ping(董宇平). Acta Chimica Sinica(化学学报)[J], 2008, 66(9): 1134—1138 [23]SHEN Jin-Bo(申进波), TONG Bin(佟斌), ZHAO Wei(赵玮), PAN Yue-Xiu(潘月秀), FENG Xiao(冯霄), SHI Jian-Bing(石建兵), ZHI Jun-Ge(支俊格), DONG Yu-Ping(董宇平). Acta Polymerica Sinica(高分子学报)[J], 2009, (8): 769—774 [24]Tong H., Dong Y. Q., Hong Y. N., Huβler M., Lam J. W. Y., Sung H. H. Y., Yu X., Sun J., Williams I. D., Kwok H. S., Tang B. Z.. J. Phys. Chem. C[J], 2007, 111(19): 2287—2294