Citation: Wu Yunying, Gou Gaozhang, Wu Xianxue, Yang Lijun, Fu Wenfu. Synthesis and Spectroscopic Properties of N, O-Chelated Pyridine-BF₂ Complexes[J]. Chinese Journal of Organic Chemistry, ;2017, 37(3): 704-710. doi: 10.6023/cjoc201607013 shu

Synthesis and Spectroscopic Properties of N, O-Chelated Pyridine-BF₂ Complexes

Wu Yunying ^a ,
Gou Gaozhang ^c ,
Wu Xianxue ^a ,
Yang Lijun ^a ,
Fu Wenfu ^b,*,,

a.
College of Resources and Environment, School of Yuxi Normal University, Yuxi 653100
b.
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190
c.
College of Science, School of Honghe University, Mengzi 661199

Corresponding author: Fu Wenfu, wuyy@yxnu.net
Received Date: 8 July 2016
Revised Date: 30 September 2016

Fund Project: the Youth Project of Science and Technology Department of Yunnan Province 2014FD50the General Program of Yunnan Provincial Education Department 2015Y455

Figures(4)

The six novel N, O-chelated pyridine-BF₂ complexes (2a~2f) were successfully obtained by a facile two-step synthesis from 2-amino-pyridine derivatives. All compounds synthesized were fully characterized by ¹H NMR, ¹³C NMR, ¹⁹F NMR, IR, ESI-MS and X-ray diffraction analysis. It was found that complexes 2b, 2c, 2e and 2f, in which electron-donating groups were substituted on p-positions of the phenyl ring (or 6-positions of the pyridine ring) exhibit a structured absorption at 360~420 nm (λ_abs=368, 400, 365, 418 nm) with a large extinction coefficient, such as 28760, 51980, 25250, 40750 L·mol^-1·cm^-1, respectively. In sharp contrast, the complexes 2a and 2d with a relatively neutral group (H for 2a) or an electron-withdrawing group (COOMe for 2d) on the p-position of the phenyl ring gave the absorption (λ_abs) blue shifted to 340 and 337 nm. Meanwhile, the intramolecular charge transfer (ICT) could be detected for complexes 2b, 2c, 2e and 2f, whose emission bands bathochromic shift significantly and emission intensities decreased with increasing the solvent polarities. Additionally, similar to most boron-dipyrromethene derivatives (BODIPYs) and their derivatives, this pyridine-BF₂ complex exhibited faint photoluminescence in the solid state. In order to better illustrate intramolecular charge transfer in 2b, 2c, 2e and 2f, theoretical calculations were carried out. Therefore, these experimental facts and theoretical calculations support our proposed ICT mechanism in the novel boron fluoride complexes 2b, 2c, 2e and 2f, and reveal that substituent groups have a significant in-fluence on optical properties. The investigations of novel pyridine-BF₂ complexes will provide favorable foundation and theo-retical support for the further development of ICT-based fluorescent dyes and their applications.
- N, O-chelated,
- pyridine,
- fluorine-boron compound,
- ICT,
- spectroscopic properties
1. [1]
2. [2]
  Kubota, Y.; Tsuzuki, T.; Funabiki, K.; Ebihara, M.; Matsui, M. Org. Lett. 2010, 12, 4010. doi: 10.1021/ol101612z
3. [3]
  (a) Nagai, A.; Kokado, K.; Nagata, Y.; Arita, M.; Chujo, Y. J. Org. Chem.2008, 73, 8605.
  (b) Poon, C.T.; Lam, W. H.; Wong, H. L.; Yam, V. W. W. J. Am. Chem. Soc. 2010, 132, 13992.
4. [4]
  (a) Claessens, C. G.; González-Rodŕguez, D.; Torres, T. Chem. Rev.2002, 102, 835.
  (b) Zhu, H.; Shimizu, S.; Kobayashi, N. Angew. Chem., Int. Ed. 2010, 49, 8000.
5. [5]
  (a) Yoshino, J.; Furuta, A.; Kambe, T.; Itoi, H.; Kano, N.; Kawashima, T.; Ito, Y.; Asashima, M.Chem.-Eur. J.2010, 16, 5026.
  (b) Yoshino, J.; Kano, N.; Kawashima, T. Chem. Commun. 2007, 6, 559.
6. [6]
  Kubota, Y.; Hara, H.; Tanaka, S.; Funabiki, K.; Matsui, M. Org. Lett. 2011, 13, 6544. doi: 10.1021/ol202819w
7. [7]
  Yang, Y.; Hughes, R. P.; Aprahamian, I. J. Am. Chem. Soc. 2014, 136, 13190. doi: 10.1021/ja508125n
8. [8]
  Liao, C. W.; Rao, M. R.; Sun, S. S. Chem. Commun. 2015, 51, 2656. doi: 10.1039/C4CC08958H
9. [9]
  Wang, X. Q.; Liu, Q. S.; Yan, H.; Liu, Z. P.; Yao, M. G.; Zhang, Q. F.; Gong, S. W.; He, W. J. Chem. Commun. 2015, 51, 7497. doi: 10.1039/C5CC01902H
10. [10]
  (a) Cosgrave, L.; Devocelle, M.; Forster, R. J.; Keyes, T. E. Chem. Commun.2010, 46, 103.
  (b) Zhang, D.; Wen, Y.; Xiao, Y.; Yu, G.; Liu, Y.; Qian, X. Chem. Commun.2008, 4777.
11. [11]
  (a) Hepp, A.; Uirich, G.; Schmechel, R.; von Seggern, H.; Ziessel, R. Synth. Met.2004, 146, 11.
  (b) Qu, X.; Liu, Q.; Ji, X.; Chen, H.; Zhou, Z.; Shen, Z. Chem. Commun.2012, 48, 4600.
12. [12]
  Martin, A.; Long, C.; Forster, R. J.; Keyes, T. E. Chem. Commun. 2012, 48, 5617. doi: 10.1039/c2cc31150j
13. [13]
  (a) Grabowski, Z. R.; Rotkiewicz, K.; Rettig, W. Chem. Rev.2003, 103, 3899.
  (b) Seo, J.; Kim, S.; Park, S. Y. J. Am. Chem. Soc.2004, 126, 11154.
  (c) Zhao, G. J.; Chen, R. K.; Sun, M. T.; Liu, J. Y.; Li, G. Y.; Gao, Y. L.; Han, K. L.; Yang, X. C.; Sun, L. Chem.-Eur. J.2008, 14, 6935.
  (d) Araneda, J. F.; Piers, W. E.; Heyne, B.; Parvez, M.; McDonald, R. Angew. Chem., Int. Ed. 2011, 50, 12214.
14. [14]
  (a) Wu, Y. Y.; Chen, Y.; Gou, G. Z.; Mu, W. H.; Lv, X. J.; Du, M. L.; Fu, W. F. Org. Lett. 2012, 14: 5226.
  (b) Wu, Y. Y.; Chen, Y.; Mu, W. H.; Lv, X. J.; Fu, W. F. J. Photochem. Photobiol. A 2013, 72, 73.
15. [15]
  Chakraborty, A.; Kar, S.; Guchhait, N. Chem. Phys. 2006, 320, 75. doi: 10.1016/j.chemphys.2005.06.031
16. [16]
  Chipem, F. A. S.; Mishra, A.; Krishnamoorthy, G. Phys. Chem. Chem. Phys. 2012, 14, 8775. doi: 10.1039/c2cp23879a
17. [17]
  Singh, T. S.; Mitra, S. J. Lumin. 2007, 127, 508. doi: 10.1016/j.jlumin.2007.03.001
18. [18]
  Sun, J. B.; Zhang, G. H.; Jia, X. Y.; Xue, P. C.; Jia, J. H.; Lu, R. Acta Chim. Sinica 2016, 74, 165 (in Chinese). doi: 10.6023/A15090628
19. [19]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuj, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr. J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene M.; Knox J. E.; Cross J. B.; Bakken V.; Adamo C.; Jaramillo J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision B.01, Gaussian, Inc., Wallingford CT, 2010.
20. [20]
  Wu, Y. X.; Ren, H. Y.; Wu, Y. F.; Wang, B. X. Acta Chim. Sinica 2015, 73, 53 (in Chinese). doi: 10.6023/A14110795
21. [21]
  Armarego, W. L. F.; Chai, C. L. L. Purification of Laboratory Chemicals, 5nd ed., Butterworth-Heinemann Press, Oxford, 2003.
1. [1]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
2. [2]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . ZnO/D-A共轭聚合物S型异质结高效光催化产H₂O₂及其电荷转移动力学研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-. doi: 10.3866/PKU.WHXB202406027
3. [3]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
4. [4]
  Hongjie SHEN , Haozhe MIAO , Yuhe YANG , Yinghua LI , Deguang HUANG , Xiaofeng ZHANG . Synthesis, crystal structure, and fluorescence properties of two Cu(Ⅰ) complexes based on pyridyl ligand. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 855-863. doi: 10.11862/CJIC.20250009
5. [5]
  Weikang Wang , Yadong Wu , Jianjun Zhang , Kai Meng , Jinhe Li , Lele Wang , Qinqin Liu . 三聚氰胺泡沫支撑的S型硫铟锌镉/硫掺杂氮化碳异质结的绿色H₂O₂合成：协同界面电荷转移调控与局域光热效应. Acta Physico-Chimica Sinica, 2025, 41(8): 100093-. doi: 10.1016/j.actphy.2025.100093
6. [6]
  Yi DING , Peiyu LIAO , Jianhua JIA , Mingliang TONG . Structure and photoluminescence modulation of silver(Ⅰ)-tetra(pyridin-4-yl)ethene metal-organic frameworks by substituted benzoates. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 141-148. doi: 10.11862/CJIC.20240393
7. [7]
  Yihao Zhao , Jitian Rao , Jie Han . Synthesis and Photochromic Properties of 3,3-Diphenyl-3H-Naphthopyran: Design and Teaching Practice of a Comprehensive Organic Experiment. University Chemistry, 2024, 39(10): 149-155. doi: 10.3866/PKU.DXHX202402050
8. [8]
  Qiaowen CHANG , Ke ZHANG , Guangying HUANG , Nuonan LI , Weiping LIU , Fuquan BAI , Caixian YAN , Yangyang FENG , Chuan ZUO . Syntheses, structures, and photo-physical properties of iridium phosphorescent complexes with phenylpyridine derivatives bearing different substituting groups. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 235-244. doi: 10.11862/CJIC.20240311
9. [9]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
10. [10]
  Hao Wu , Zhen Liu , Dachang Bai . ¹H NMR Spectrum of Amide Compounds. University Chemistry, 2024, 39(3): 231-238. doi: 10.3866/PKU.DXHX202309020
11. [11]
  Qianlang Wang , Jijun Sun , Qian Chen , Quanqin Zhao , Baojuan Xi . The Appeal of Organophosphorus Compounds: Clearing Their Name. University Chemistry, 2025, 40(4): 299-306. doi: 10.12461/PKU.DXHX202405205
12. [12]
  Jiajie Cai , Chang Cheng , Bowen Liu , Jianjun Zhang , Chuanjia Jiang , Bei Cheng . CdS/DBTSO-BDTO S型异质结光催化制氢及其电荷转移动力学. Acta Physico-Chimica Sinica, 2025, 41(8): 100084-. doi: 10.1016/j.actphy.2025.100084
13. [13]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
14. [14]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
15. [15]
  Yahui HAN , Jinjin ZHAO , Ning REN , Jianjun ZHANG . Synthesis, crystal structure, thermal decomposition mechanism, and fluorescence properties of benzoic acid and 4-hydroxy-2, 2′: 6′, 2″-terpyridine lanthanide complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 969-982. doi: 10.11862/CJIC.20240395
16. [16]
  Chen LU , Qinlong HONG , Haixia ZHANG , Jian ZHANG . Syntheses, structures, and properties of copper-iodine cluster-based boron imidazolate framework materials. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 149-154. doi: 10.11862/CJIC.20240407
17. [17]
  Yi Yang , Xin Zhou , Miaoli Gu , Bei Cheng , Zhen Wu , Jianjun Zhang . Femtosecond transient absorption spectroscopy investigation on ultrafast electron transfer in S-scheme ZnO/CdIn₂S₄ photocatalyst for H₂O₂ production and benzylamine oxidation. Acta Physico-Chimica Sinica, 2025, 41(6): 100064-. doi: 10.1016/j.actphy.2025.100064
18. [18]
  Peng Li , Yuanying Cui , Zhongliao Wang , Graham Dawson , Chunfeng Shao , Kai Dai . Efficient interfacial charge transfer of CeO₂/Bi₁₉Br₃S₂₇ S-scheme heterojunction for boosted photocatalytic CO₂ reduction. Acta Physico-Chimica Sinica, 2025, 41(6): 100065-. doi: 10.1016/j.actphy.2025.100065
19. [19]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
20. [20]
  Ying Xiong , Guangao Yu , Lin Wu , Qingwen Liu , Houjin Li , Shuanglian Cai , Zhanxiang Liu , Xingwen Sun , Yuan Zheng , Jie Han , Xin Du , Chengshan Yuan , Qihan Zhang , Jianrong Zhang , Shuyong Zhang . Basic Operations and Specification Suggestions for Determination of Physical Constants of Organic Compounds. University Chemistry, 2025, 40(5): 106-121. doi: 10.12461/PKU.DXHX202503079

Get Citation

PDF

XML

Metrics

PDF Downloads(20)
Abstract views(2031)
HTML views(199)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis and Spectroscopic Properties of N, O-Chelated Pyridine-BF2 Complexes

Metrics

通讯作者: 陈斌, bchen63@163.com

Synthesis and Spectroscopic Properties of N, O-Chelated Pyridine-BF₂ Complexes