Citation: Qin Yanyan, She Pengfei, Guo Song, Huang Xiaomeng, Liu Shujuan, Zhao Qiang, Huang Wei. Structural Manipulation and Triboluminescence of Tetrahalomanganese(Ⅱ) Complexes[J]. Acta Physico-Chimica Sinica, ;2020, 36(1): 190707. doi: 10.3866/PKU.WHXB201907078 shu

Structural Manipulation and Triboluminescence of Tetrahalomanganese(Ⅱ) Complexes

Qin Yanyan ¹ ,
She Pengfei ¹ ,
Guo Song ¹ ,
Huang Xiaomeng ¹ ,
Liu Shujuan ¹ ,
Zhao Qiang ^1,, ,
Huang Wei ^1,2,,

1.
Institute of Advanced Materials, Key Laboratory for Organic Electronics and Information Displays, Nanjing University of Posts & Telecommunications, Nanjing 210023, P. R. China
2.
Shaanxi Institute of Flexible Electronics, Northwestern Polytechnical University, Xi'an 710072, P. R. China

Corresponding author: Zhao Qiang, iamqzhao@njupt.edu.cn Huang Wei, provost@nwpu.edu.cn
Received Date: 25 July 2019
Revised Date: 2 September 2019
Accepted Date: 3 September 2019
Available Online: 10 January 2019
Fund Project: the China Postdoctoral Science Foundation 2018M642282The project was supported by the National Funds for Distinguished Young Scientists, China (61825503), the China Postdoctoral Science Foundation (2018M642282), the Natural Science Foundation of Jiangsu Province, China (BK20180760) and the Jiangsu Planned Projects for Postdoctoral Research Funds, China (2018K155C)the Natural Science Foundation of Jiangsu Province, China BK20180760the National Funds for Distinguished Young Scientists, China 61825503the Jiangsu Planned Projects for Postdoctoral Research Funds, China 2018K155C

Triboluminescence is a fascinating luminescence phenomenon induced by mechanical stimuli. Triboluminescent materials have potential applications in lighting, displays, and sensing, owing to their distinctive modes of light generation. However, organic triboluminescent materials are severely limited, and their luminescence mechanism remains unclear. Herein, we found that the luminescent manganese(Ⅱ) complex [BPP]₂[MnBr₄] displayed interesting triboluminescence performance. A series of green emissive tetrahalomanganese(Ⅱ) complexes was rationally designed and synthesized. The associated single crystal structures revealed that all complexes consisted of one [MnX₄]²⁻ (X = Br or Cl) ion and two organic cationic ligands per unit cell, with a tetrahedral geometrical symmetry around the Mn(Ⅱ) ion. In addition, the photophysical properties of tetrahalomanganese(Ⅱ) complexes were easily tuned by varying the organic ligands or halogen ions, which is beneficial for these organic-inorganic hybrid structures. Under UV light irradiation, all tetrahalomanganese(Ⅱ) complexes in the solid state exhibited bright green luminescence and a broad featureless emission band at 450–650 nm. The time-resolved photoluminescent decay curves demonstrated that the emission lifetimes of the prepared tetrahalomanganese(Ⅱ) complexes ranged from 260.5 μs to 1.95 ms, which was attributed to phosphorescence. The long-lived emission was mainly due to the spin-forbidden nature of the metal center d–d (⁴T₁(G)→ ⁶A₁) radiative transition. Thermogravimetric analysis was performed to examine the thermodynamic stabilities of the tetrahalomanganese(Ⅱ) complexes. The thermal stabilities of manganese(Ⅱ) complexes with P-based ligands were higher than those of the complexes containing N-based ligands. Upon applying a force to the crystals, the tetrahalomanganese(Ⅱ) complexes all exhibited prominent triboluminescence that could be observed by the naked eye in the dark. Systematic analysis of the crystals showed that the TL activities of the manganese(Ⅱ) complexes were related to the intra- and inter-molecular C-H···X (X = Br or Cl) interactions. The intra- and inter-molecular C-H···X interactions significantly reduced the possible energy loss caused by molecular vibrations and rotations in the [MnX₄]²⁻ unit under mechanical stress, improving TL emission. Moreover, a comparison of photoluminescence and triboluminescence indicated that different excitation sources yielded two distinct luminescence processes: transition of excitons excited by illumination and recombination of electrons and holes on the surface driven by polarization charges. Overall, the results presented herein new opportunities for fundamental research based on the developed class of triboluminescent materials.
- Triboluminescence,
- Manganese(Ⅱ) complex,
- Green-light emission,
- Phosphorescence,
- Intra-/inter-molecular interaction
1. [1]
  Sage, I.; Bourhill, G. J. Mater. Chem. 2001, 11, 231. doi: 10.1039/b007029g doi: 10.1039/b007029g
2. [2]
  Olawale, D. O.; Dickens, T.; Sullivan, W. G.; Okoli, O. I.; Sobanjo, J. O.; Wang, B. J. Lumin. 2011, 131, 1407. doi: 10.1016/j.jlumin.2011.03.015 doi: 10.1016/j.jlumin.2011.03.015
3. [3]
  Eddingsaas, N. C.; Suslick, K. S. J. Am. Chem. Soc. 2007, 129, 6718. doi: 10.1021/ja0716498 doi: 10.1021/ja0716498
4. [4]
  Wang, X. D.; Zhang, H. L.; Yu, R. M.; Dong, L.; Peng, D. F.; Zhang, A. H.; Zhang, Y.; Liu, H.; Pan, C. F.; Wang, Z. L. Adv. Mater. 2015, 27, 2324. doi: 10.1002/adma.201405826 doi: 10.1002/adma.201405826
5. [5]
  Li, W. L.; Huang, Q. Y.; Mao, Z.; Li, Q.; Jiang, L.; Xie, Z. L.; Xu, R.; Yang, Z. Y.; Zhao, J.; Yu, T.; et al. Angew. Chem. Int. Ed. 2018, 57, 12727. doi: 10.1002/anie.201806861 doi: 10.1002/anie.201806861
6. [6]
  Yang, J.; Ren, Z. C.; Xie, Z. L.; Liu, Y. J.; Wang, C.; Xie, Y. J.; Peng, Q.; Xu, B.; Tian, W. J.; Zhang, F.; et al. Angew. Chem. Int. Ed. 2017, 56, 880. doi: 10.1002/anie.201610453 doi: 10.1002/anie.201610453
7. [7]
  Wong, H. Y.; Lo, W. S.; Chan, W. T. K.; Law G. L. Inorg. Chem. 2017, 56, 5135. doi: 10.1021/acs.inorgchem.7b00273 doi: 10.1021/acs.inorgchem.7b00273
8. [8]
  Hirai, Y.; Nakanishi, T.; Kitagawa, Y.; Fushimi, K.; Seki, T.; Ito, H.; Hasegawa, Y. Angew. Chem. Int. Ed. 2017, 56, 7171. doi: 10.1002/anie.201703638 doi: 10.1002/anie.201703638
9. [9]
  Hirai, Y.; da Rosa, P. P. F.; Nakanishi, T.; Kitagawa, Y.; Fushimi, K.; Seki, T.; Ito, H.; Hasegawa, Y. Inorg. Chem. 2018, 57, 14653. doi: 10.1021/acs.inorgchem.8b02367 doi: 10.1021/acs.inorgchem.8b02367
10. [10]
  Xie, Z. L.; Yu, T.; Chen, J. R.; Ubba, E.; Wang, L. Y.; Mao, Z.; Su, T. T.; Zhang, Y.; Aldred, M. P.; Chi, Z. G. Chem. Sci. 2018, 9, 5787. doi: 10.1039/c8sc01703d doi: 10.1039/c8sc01703d
11. [11]
  Wang, J. Q.; Wang, C.; Gong, Y. B.; Liao, Q. Y.; Han, M. M.; Jiang, T. J.; Dang, Q. X.; Li, Y. Q.; Li, Q. Q.; Li, Z. Angew. Chem. Int. Ed. 2018, 57, 16821. doi: 10.1002/anie.201811660 doi: 10.1002/anie.201811660
12. [12]
  Yang, J.; Gao, X. M.; Xie, Z. L.; Gong, Y. B.; Fang, M. M.; Peng, Q.; Chi, Z. G.; Li, Z. Angew. Chem. Int. Ed. 2017, 56, 15299. doi: 10.1002/anie.201708119 doi: 10.1002/anie.201708119
13. [13]
  Yang, J.; Qin, J. W.; Geng, P. Y.; Wang, J. Q.; Fang, M. M.; Li, Z. Angew. Chem. Int. Ed. 2018, 57, 14174. doi: 10.1002/anie.201809463 doi: 10.1002/anie.201809463
14. [14]
  Marchetti, F.; Nicola, D. C.; Pettinari, R.; Timokhin, I.; Pettinari, C. J. Chem. Educ. 2012, 89, 652. doi: 10.1021/ed2001494 doi: 10.1021/ed2001494
15. [15]
  Wrighton, M.; Ginley, D. Chem. Phys. 1974, 4, 295. doi: 10.1016/0301-0104(74)80097-2 doi: 10.1016/0301-0104(74)80097-2
16. [16]
  Cotton, F. A.; Goodgame, D. M. L.; Goodgame, M. J. Am. Chem. Soc. 1962, 84, 167. doi: 10.1021/ja00861a008 doi: 10.1021/ja00861a008
17. [17]
  Hardy, G. E.; Zink, J. I. Inorg. Chem. 1976, 15, 3061. doi: 10.1021/ic50166a026 doi: 10.1021/ic50166a026
18. [18]
  Pitula, S.; Mudring, A. V. Chem. Eur. J. 2010, 16, 3355. doi: 10.1002/chem.200802660 doi: 10.1002/chem.200802660
19. [19]
  Zhang, Y.; Liao, W. Q.; Fu, D. W.; Ye, H. Y.; Liu, C. M.; Chen, Z. N.; Xiong, R. G. Adv. Mater. 2015, 27, 3942. doi: 10.1002/adma.201501026 doi: 10.1002/adma.201501026
20. [20]
  Bortoluzzi, M.; Castro, J.; Enrichi, F.; Vomiero, A.; Busato, M.; Huang, W. Z. Inorg. Chem. Commun. 2018, 92, 145. doi: 10.1016/j.inoche.2018.04.023 doi: 10.1016/j.inoche.2018.04.023
21. [21]
  Hausmann, D.; Kuzmanoski A.; Feldmann, C. Dalton Trans. 2016, 45, 6541. doi: 10.1039/c6dt00458j doi: 10.1039/c6dt00458j
22. [22]
  Berezin, A. S.; Samsonenko, D. G.; Brel, V. K.; Artem'ev, A. V. Dalton Trans. 2018, 47, 7306. doi: 10.1039/c8dt01041b doi: 10.1039/c8dt01041b
23. [23]
  Wu, Y.; Zhang, X.; Xu, L. J.; Yang, M.; Chen, Z. N. Inorg. Chem. 2018, 57, 9175. doi: 10.1021/acs.inorgchem.8b01205 doi: 10.1021/acs.inorgchem.8b01205
24. [24]
  Xu, L. J.; Sun, C. Z.; Xiao, H.; Wu, Y.; Chen, Z. N. Adv. Mater. 2017, 29, 1605739. doi: 10.1002/adma.201605739 doi: 10.1002/adma.201605739
25. [25]
  Qin, Y. Y.; Tao, P.; Gao, L.; She, P. F.; Liu, S. J.; Li, X. L.; Li, F. Y.; Wang, H.; Zhao, Q.; Miao, Y. Q.; et al. Adv. Optical Mater. 2019, 7, 1801160. doi: 10.1002/adom.201801160 doi: 10.1002/adom.201801160
26. [26]
  Cotton, F. A.; Daniels, L. M.; Huang, P. L. Inorg. Chem. 2001, 40, 3576. doi: 10.1021/ic0101836 doi: 10.1021/ic0101836
27. [27]
  Balsamy, S.; Natarajan, P.; Vedalakshmi, R.; Muralidharan, S. Inorg. Chem. 2014, 53, 6054. doi: 10.1021/ic500400y doi: 10.1021/ic500400y
28. [28]
  Chen, J.; Zhang, Q.; Zheng, F. K.; Liu, Z. F.; Wang, S. H.; Wu, A. Q.; Guo, G. C. Dalton Trans. 2015, 44, 3289. doi: 10.1039/c4dt03694h doi: 10.1039/c4dt03694h
29. [29]
  Jiang, D. M.; Bo, L.; Zhu, T.; Tao, J. B.; Yang. X. P. Acta Phys. -Chim. Sin. 2018, 34, 812. doi: 10.3866/PKU.WHXB201801086
30. [30]
  Xia, H. Y.; Geng, T.; Zhao, Xu.; Li, F. F.; Wang, F. Y.; Gao, L. N. Acta Phys. -Chim. Sin. 2019, 35, 337. doi: 10.3866/PKU.WHXB201803082
1. [1]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
2. [2]
  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
3. [3]
  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
4. [4]
  Changqing MIAO , Fengjiao CHEN , Wenyu LI , Shujie WEI , Yuqing YAO , Keyi WANG , Ni WANG , Xiaoyan XIN , Ming FANG . Crystal structures, DNA action, and antibacterial activities of three tetranuclear lanthanide-based complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2455-2465. doi: 10.11862/CJIC.20240192
5. [5]
  Cheng Zheng , Shiying Zheng , Yanping Zhang , Shoutian Zheng , Qiaohua Wei . Synthesis, Copper Content Analysis, and Luminescent Performance Study of Binuclear Copper (I) Complexes with Isomeric Luminescence Shift: A Comprehensive Chemical Experiment Recommendation. University Chemistry, 2024, 39(7): 322-329. doi: 10.3866/PKU.DXHX202310131
6. [6]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
7. [7]
  Yang YANG , Pengcheng LI , Zhan SHU , Nengrong TU , Zonghua WANG . Plasmon-enhanced upconversion luminescence and application of molecular detection. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 877-884. doi: 10.11862/CJIC.20230440
8. [8]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
9. [9]
  Xiaowei TANG , Shiquan XIAO , Jingwen SUN , Yu ZHU , Xiaoting CHEN , Haiyan ZHANG . A zinc complex for the detection of anthrax biomarker. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1850-1860. doi: 10.11862/CJIC.20240173
10. [10]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
11. [11]
  Shuang Meng , Haixin Long , Zhou Zhou , Meizhu Rong . Inorganic Chemistry Curriculum Design and Implementation of Based on “Stepped-Task Driven + Multi-Dimensional Output” Model: A Case Study on Intermolecular Forces. University Chemistry, 2024, 39(3): 122-131. doi: 10.3866/PKU.DXHX202309008
12. [12]
  Qilu DU , Li ZHAO , Peng NIE , Bo XU . Synthesis and characterization of osmium-germyl complexes stabilized by triphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1088-1094. doi: 10.11862/CJIC.20240006
13. [13]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188
14. [14]
  Wei Li , Ze Chang , Meihui Yu , Ying Zhang . Curriculum Ideological and Political Design of Piezoelectricity Measurement Experiments of Coordination Compounds. University Chemistry, 2024, 39(2): 77-82. doi: 10.3866/PKU.DXHX202308004
15. [15]
  Ji Qi , Jianan Zhu , Yanxu Zhang , Jiahao Yang , Chunting Zhang . Visible Color Change of Copper (II) Complexes in Reversible SCSC Transformation: The Effect of Structure on Color. University Chemistry, 2024, 39(3): 43-57. doi: 10.3866/PKU.DXHX202307050
16. [16]
  Cunling Ye , Xitong Zhao , Hongfang Wang , Zhike Wang . A Formula for the Calculation of Complex Concentrations Arising from Side Reactions and Its Applications. University Chemistry, 2024, 39(4): 382-386. doi: 10.3866/PKU.DXHX202310043
17. [17]
  Keweiyang Zhang , Zihan Fan , Liyuan Xiao , Haitao Long , Jing Jing . Unveiling Crystal Field Theory: Preparation, Characterization, and Performance Assessment of Nickel Macrocyclic Complexes. University Chemistry, 2024, 39(5): 163-171. doi: 10.3866/PKU.DXHX202310084
18. [18]
  Wenjing ZHANG , Xiaoqing WANG , Zhipeng LIU . Recent developments of inorganic metal complex-based photothermal materials and their applications in photothermal therapy. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2356-2372. doi: 10.11862/CJIC.20240254
19. [19]
  Qingjun PAN , Zhongliang GONG , Yuwu ZHONG . Advances in modulation of the excited states of photofunctional iron complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 45-58. doi: 10.11862/CJIC.20240365
20. [20]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207

Get Citation

PDF

XML

Metrics

PDF Downloads(17)
Abstract views(261)
HTML views(26)

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