Citation: Pengfei Li, Chulin Qu, Fan Wu, Hu Gao, Chengyan Zhao, Yue Zhao, Zhen Shen. Robust free-base and metalated corrole radicals with reduction-induced emission[J]. Chinese Chemical Letters, ;2025, 36(2): 110292. doi: 10.1016/j.cclet.2024.110292 shu

Robust free-base and metalated corrole radicals with reduction-induced emission

Pengfei Li ^a ,
Chulin Qu ^a ,
Fan Wu ^{a, b, *,} ,
Hu Gao ^{a, c} ,
Chengyan Zhao ^a ,
Yue Zhao ^a ,
Zhen Shen ^{a, *,}

a.
State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
b.
School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China
c.
College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China

wufan@nnu.edu.cn

zshen@nju.edu.cn

Received Date: 23 May 2024
Revised Date: 14 July 2024
Accepted Date: 23 July 2024
Available Online: 23 July 2024

Figures(6)

Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task. Here we report the synthesis of a stable, free-base benzocorrole (BC) radical containing only two inner NH protons via a retro-Diels-Alder conversion. The radical character of BC was fully supported by crystallographic analysis, spectroscopic evidence, and theoretical calculations. This neutral radical ligand allowed easy insertion of Zn(Ⅱ), Ga(Ⅲ), and Pd(Ⅱ) ions to produce radical complexes. All these radicals exhibited luminescence-on responses under weak reducing atmosphere, corresponding to the conversion to their aromatic anions. The red fluorescence was observed for BC and its Zn(Ⅱ) and Ga(Ⅲ) complexes, and the near-infrared phosphorescence (> 900 nm) was detected for Pd(Ⅱ) complex at room temperature. Furthermore, Ga(Ⅲ) corrole exhibited a variation in fluorescence in response to axial coordination. Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.
- Radicals,
- Porphyrinoids,
- Macrocyclic ligands,
- Luminescence,
- Redox chemistry
1. [1]
  Z.X. Chen, Y. Li, F. Huang, Chem 7 (2021) 288–332. doi: 10.1016/j.chempr.2020.09.024
2. [2]
  L. Ji, J. Shi, J. Wei, et al., Adv. Mater. 32 (2020) 1908015. doi: 10.1002/adma.201908015
3. [3]
  I. Ratera, J. Veciana, Chem. Soc. Rev. 41 (2012) 303–349. doi: 10.1039/C1CS15165G
4. [4]
  D. Shimizu, A. Osuka, Chem. Sci. 9 (2018) 1408–1423. doi: 10.1039/c7sc05210c
5. [5]
  D. Shimizu, J. Oh, K. Furukawa, et al., Angew. Chem. Int. Ed. 54 (2015) 6613–6617. doi: 10.1002/anie.201501592
6. [6]
  W. Deng, Y. Liu, D. Shimizu, et al., Chem. Eur. J. 29 (2023) e202203484. doi: 10.1002/chem.202203484
7. [7]
  T. Yoshida, W. Zhou, T. Furuyama, et al., J. Am. Chem. Soc. 137 (2015) 9258–9261. doi: 10.1021/jacs.5b05781
8. [8]
  D. Shimizu, K. Fujimoto, A. Osuka, Angew. Chem. Int. Ed. 57 (2018) 9434–9438. doi: 10.1002/anie.201805385
9. [9]
  N. Fukui, W. Cha, D. Shimizu, et al., Chem. Sci. 8 (2017) 189–199. doi: 10.1039/C6SC02721K
10. [10]
  X.-S. Ke, Y. Hong, P. Tu, et al., J. Am. Chem. Soc. 139 (2017) 15232–15238. doi: 10.1021/jacs.7b09167
11. [11]
  J. Shen, J. Shao, Ou Z, et al., Inorg. Chem. 45 (2006) 2251–2265. doi: 10.1021/ic051729h
12. [12]
  Y. Yamamoto, A. Yamamoto, Shin-ya Furuta, et al., J. Am. Chem. Soc. 127 (2005) 14540–14541. doi: 10.1021/ja052842+
13. [13]
  Y. Yamamoto, Y. Hirata, M. Kodama, et al., J. Am. Chem. Soc. 132 (2010) 12627–12638. doi: 10.1021/ja102817a
14. [14]
  D. Shimizu, J. Oh, K. Furukawa, et al., J. Am. Chem. Soc. 137 (2015) 15584–15594. doi: 10.1021/jacs.5b11223
15. [15]
  P. Schweyen, K. Brandhorst, R. Wicht, et al., Angew. Chem. Int. Ed. 54 (2015) 8213–8216. doi: 10.1002/anie.201503624
16. [16]
  S. Hiroto, H. Shinokubo, A. Osuka, J. Am. Chem. Soc. 128 (2006) 6568–6569. doi: 10.1021/ja061621g
17. [17]
  S. Ooi, D. Shimizu, K. Furukawa, et al., Angew. Chem. Int. Ed. 57 (2018) 14916–14920. doi: 10.1002/anie.201810200
18. [18]
  S. Ooi, B. Adinarayana, D. Shimizu, et al., Angew. Chem. Int. Ed. 59 (2020) 9423–9427. doi: 10.1002/anie.202002976
19. [19]
  A. Ghosh, Chem. Rev. 117 (2017) 3798–3881. doi: 10.1021/acs.chemrev.6b00590
20. [20]
  H. Gao, F. Wu, Y. Zhao, et al., J. Am. Chem. Soc. 144 (2022) 3458–3467. doi: 10.1021/jacs.1c11716
21. [21]
  M.L. Naitana, W.R. Osterloh, L. Di Zazzo, et al., Inorg. Chem. 61 (2022) 17790–17803. doi: 10.1021/acs.inorgchem.2c03099
22. [22]
  C.M. Lemon, M. Huynh, A.G. Maher, et al., Angew. Chem. Int. Ed. 55 (2016) 2176–2180. doi: 10.1002/anie.201509099
23. [23]
  A.B. Alemayehu, H. Vazquez-Lima, C.M. Beavers, et al., Chem. Commun. 50 (2014) 11093–11096. doi: 10.1039/C4CC02548B
24. [24]
  R.D. Teo, J.Y. Hwang, J. Termini, et al., Chem. Rev. 117 (2017) 2711–2729. doi: 10.1021/acs.chemrev.6b00400
25. [25]
  H. Gao, X. Zhi, F. Wu, et al., Angew. Chem. Int. Ed. 62 (2023) e202309208. doi: 10.1002/anie.202309208
26. [26]
  L. Shi, H.Y. Liu, L.P. Si, et al., Chin. Chem. Lett. 21 (2010) 373–375. doi: 10.1016/j.cclet.2009.11.027
27. [27]
  H. Shi, R. Liang, D.L. Phillips, et al., J. Am. Chem. Soc. 144 (2022) 7588–7593. doi: 10.1021/jacs.2c02506
28. [28]
  Q.-C. Chen, S. Fite, N. Fridman, et al., ACS Catal. 12 (2022) 4310–4317. doi: 10.1021/acscatal.1c05243
29. [29]
  N.C. Ng, M.H.R. Mahmood, H.Y. Liu, et al., Chin. Chem. Lett. 25 (2014) 571–574. doi: 10.1016/j.cclet.2014.01.027
30. [30]
  L. Yu, Q. Wang, L. Dai, et al., Chin. Chem. Lett. 24 (2013) 447–449. doi: 10.1016/j.cclet.2013.03.029
31. [31]
  C. Wu, X. Li, M. Shao, et al., Chin. Chem. Lett. 33 (2022) 4559–4562. doi: 10.1016/j.cclet.2022.01.065
32. [32]
  Q. Zhang, Y. Wang, Y. Wang, et al., Chin. Chem. Lett. 32 (2021) 3807–3810. doi: 10.1016/j.cclet.2021.04.048
33. [33]
  Y. Zhang, K. Ren, L. Wang, et al., Chin. Chem. Lett. 33 (2022) 33–60. doi: 10.1016/j.cclet.2021.06.013
34. [34]
  F. Wu, J. Liu, P. Mishra, et al., Nat. Commun. 6 (2015) 7547. doi: 10.1038/ncomms8547
35. [35]
  J. Xu, L. Zhu, H. Gao, et al., Angew. Chem. Int. Ed. 60 (2021) 11702–11706. doi: 10.1002/anie.202016674
36. [36]
  F. Wu, H. Gao, Y. Zhao, et al., Chin. Chem. Lett. 34 (2023) 107994. doi: 10.1016/j.cclet.2022.107994
37. [37]
  C. Yu, H. Xiao, H. Lu, et al., Chin. Chem. Lett. 35 (2024) 108883. doi: 10.1016/j.cclet.2023.108883
38. [38]
  G. Pomarico, S. Nardis, R. Paolesse, et al., J. Org. Chem. 76 (2011) 3765–3773. doi: 10.1021/jo200026u
39. [39]
  G. Pomarico, S. Nardis, M.L. Naitana, et al., Inorg. Chem. 52 (2013) 4061–4070. doi: 10.1021/ic400162y
40. [40]
  S. Ito, T. Murashima, N. Ono, et al., Chem. Commun. (1998) 1661–1662. doi: 10.1039/A803656J
41. [41]
  Z. Gross, N. Galili, L. Simkhovich, et al., Org. Lett. 1 (1999) 599–602. doi: 10.1021/ol990739h
42. [42]
  T. Ding, J.D. Harvey, C.J. Ziegler, J. Porphyr. Phthalocyanines 09 (2005) 22–27. doi: 10.1142/S1088424605000058
43. [43]
  J. Capar, J. Conradie, C.M. Beavers, et al., J. Phys. Chem. 119 (2015) 3452–3457. doi: 10.1021/jp511188c
44. [44]
  Y. Fang, Z. Ou, K.M. Kadish, Chem. Rev. 117 (2017) 3377–3419. doi: 10.1021/acs.chemrev.6b00546
45. [45]
  Y. Fang, M.O. Senge, E. Van Caemelbecke, et al., Inorg. Chem. 53 (2014) 10772–10778. doi: 10.1021/ic502162p
46. [46]
  J. Gaŕate-Morales, F. Tham, C. Reed, et al., Inorg. Chem. 46 (2007) 1514–1516. doi: 10.1021/ic062213g
47. [47]
  S. Fukuzumi, T. Honda, T. Kojima, Coord. Chem. Rev. 256 (2012) 2488–2502. doi: 10.1016/j.ccr.2012.01.011
48. [48]
  C.M. Lemon, R.L. Halbach, M. Huynh, et al., Inorg. Chem. 54 (2015) 2713–2725. doi: 10.1021/ic502860g
49. [49]
  T. Naito, A. saito, M. Ueda, et al., Heterocycles 65 (2005) 1857–1869. doi: 10.3987/COM-05-10426
50. [50]
  D.Y. Jeong, D.S. Lee, H.L. Lee, et al., ACS Catal. 12 (2022) 6047–6059. doi: 10.1021/acscatal.2c00763
51. [51]
  S. Xu, F. Yang, H. Fan, et al., New J. Chem. 46 (2022) 9994–9998. doi: 10.1039/d2nj00341d
52. [52]
  D. Shen, T. Ren, Z. Luo, et al., Org. Biomol. Chem. 21 (2023) 4955–4961. doi: 10.1039/d3ob00663h
53. [53]
  J. Mack, M.J. Stillman, N. Kobayashi, Coord. Chem. Rev. 251 (2007) 429–453. doi: 10.1016/j.ccr.2006.05.011
54. [54]
  J. Helaja, M. Stapelbroek-Mo¨llmann, I. Kilpela¨inen, et al., J. Org. Chem. 65 (2000) 3700–3707. doi: 10.1021/jo9918955
55. [55]
  A. Mahammed, J.J. Weaver, H.B. Gray, et al., Tetrahedron Lett. 44 (2003) 2077–2079. doi: 10.1016/S0040-4039(03)00174-6
56. [56]
  A. Ghosh, T. Wondimagegn, A.B.J. Parusel, J. Am. Chem. Soc. 122 (2000) 5100–5104. doi: 10.1021/ja9943243
57. [57]
  Z. Liu, T. Lu, Q. Chen, Carbon 165 (2020) 461–467. doi: 10.1016/j.carbon.2020.05.023
58. [58]
  S. Klod, E. Kleinpeter, J. Chem. Soc., Perkin Trans. 2. 10 (2001) 1893–1898. doi: 10.1039/B009809O
59. [59]
  T. Lu, F. Chen, J. Comput. Chem. 33 (2012) 580–592. doi: 10.1002/jcc.22885
60. [60]
  A. Mahammed, J.J. Weaver, H.B. Gray, et al., Tetrahedron Lett. 44 (2003) 2077–2079. doi: 10.1016/S0040-4039(03)00174-6
61. [61]
  Z. Chen, C. Wannere, C. Corminboeuf, et al., Chem. Rev. 105 (2005) 3842–3888. doi: 10.1021/cr030088+
62. [62]
  D. Geuenich, K. Hess, F. Köhler, et al., Chem. Rev. 105 (2005) 3758–3772. doi: 10.1021/cr0300901
63. [63]
  I. Aviv-Harel, Z. Gross, Coord. Chem. Rev. 255 (2011) 717–736. doi: 10.1016/j.ccr.2010.09.013
64. [64]
  M. Pribisko, J. Palmer, R.H. Grubbs, et al., Proc. Natl. Acad. Sci. U. S. A. 113 (2016) E2258–E2266. doi: 10.1073/pnas.1525564113
65. [65]
  L.G. Liu, Y.M. Sun, Z.Y. Liu, et al., Inorg. Chem. 60 (2021) 2234–2245. doi: 10.1021/acs.inorgchem.0c03016
66. [66]
  J. Bendix, I.J. Dmochowski, H.B. Gray, et al., Angew. Chem. Int. Ed. 39 (2000) 4048–4051. doi: 10.1002/1521-3773(20001117)39:22<4048::AID-ANIE4048>3.0.CO;2-7
67. [67]
  B. Basumatary, J. Rai, R.V.R. Reddy, et al., Chem. Eur. J. 23 (2017) 17458–17462. doi: 10.1002/chem.201704457
68. [68]
  Q.C. Chen, N. Fridman, Y. Diskin-Posner, et al., Chem. Eur. J. 26 (2020) 9481–9485. doi: 10.1002/chem.202002682
69. [69]
  F. Neese, WIREs Comp. Mol. Sci. 2 (2011) 73–78. doi: 10.1002/wcms.81
70. [70]
  F. Neese, WIREs Comp. Mol. Sci. 12 (2022) e1606. doi: 10.1002/wcms.1606
71. [71]
  W. Zhao, Z. He, B.Z. Tang, Nat. Rev. Mater. 5 (2020) 869–885. doi: 10.1038/s41578-020-0223-z
1. [1]
  Hao Jiang , Yuan-Yuan He , Hai-Chao Liang , Meng-Jia Shang , Han-Han Lu , Chun-Hua Liu , Yin-Shan Meng , Tao Liu , Yuan-Yuan Zhu . Tuning lanthanide luminescence from bipyridine-bis(oxazoline/thiazoline) tetradentate ligands. Chinese Journal of Structural Chemistry, 2024, 43(9): 100354-100354. doi: 10.1016/j.cjsc.2024.100354
2. [2]
  Chun-Yun Ding , Ru-Yuan Zhang , Yu-Wu Zhong , Jiannian Yao . Binary and heterostructured microplates of iridium and ruthenium complexes: Preparation, characterization, and thermo-responsive emission. Chinese Journal of Structural Chemistry, 2024, 43(10): 100393-100393. doi: 10.1016/j.cjsc.2024.100393
3. [3]
  Pan Liu , Yanming Sun , Alberto J. Fernández-Carrión , Bowen Zhang , Hui Fu , Lunhua He , Xing Ming , Congling Yin , Xiaojun Kuang . Bismuth-based halide double perovskite Cs₂KBiCl₆: Disorder and luminescence. Chinese Chemical Letters, 2024, 35(5): 108641-. doi: 10.1016/j.cclet.2023.108641
4. [4]
  Yan Cheng , Hua-Peng Ruan , Yan Peng , Longhe Li , Zhenqiang Xie , Lang Liu , Shiyong Zhang , Hengyun Ye , Zhao-Bo Hu . Magnetic, dielectric and luminescence synergetic switchable effects in molecular material [Et₃NCH₂Cl]₂[MnBr₄]. Chinese Chemical Letters, 2024, 35(4): 108554-. doi: 10.1016/j.cclet.2023.108554
5. [5]
  Xiangshuai Li , Jian Zhao , Li Luo , Zhuohao Jiao , Ying Shi , Shengli Hou , Bin Zhao . Visual and portable detection of metronidazole realized by metal-organic framework flexible sensor and smartphone scanning. Chinese Chemical Letters, 2024, 35(10): 109407-. doi: 10.1016/j.cclet.2023.109407
6. [6]
  Zhu Shu , Xin Lei , Yeye Ai , Ke Shao , Jianliang Shen , Zhegang Huang , Yongguang Li . ATP-induced supramolecular assembly based on chromophoric organic molecules and metal complexes. Chinese Chemical Letters, 2024, 35(11): 109585-. doi: 10.1016/j.cclet.2024.109585
7. [7]
  Wen-Jun Xia , Yong-Jiang Wang , Yun-Fei Cao , Cai Sun , Xin-Xiong Li , Yan-Qiong Sun , Shou-Tian Zheng . A luminescent folded S-shaped high-nuclearity Eu₁₉-oxo-cluster embedded polyoxoniobate for information encryption. Chinese Chemical Letters, 2025, 36(2): 110248-. doi: 10.1016/j.cclet.2024.110248
8. [8]
  Jindan Zhang , Zhenghong Li , Chi Li , Mengqi Zhu , Shicheng Tang , Kaicong Cai , Zhibin Cheng , Chulong Liu , Shengchang Xiang , Zhangjing Zhang . Revealing a new doping mechanism of spiro-OMeTAD with tBP participation through the introduction of radicals into HTM. Chinese Chemical Letters, 2025, 36(3): 110046-. doi: 10.1016/j.cclet.2024.110046
9. [9]
  Shihong Wu , Ronghui Zhou , Hang Zhao , Peng Wu . Sonoafterglow luminescence for in vivo deep-tissue imaging. Chinese Chemical Letters, 2024, 35(10): 110026-. doi: 10.1016/j.cclet.2024.110026
10. [10]
  Jian-Rong Li , Jieying Hu , Lai-Hon Chung , Jilong Zhou , Parijat Borah , Zhiqing Lin , Yuan-Hui Zhong , Hua-Qun Zhou , Xianghua Yang , Zhengtao Xu , Jun He . Insight into stable, concentrated radicals from sulfur-functionalized alkyne-rich crystalline frameworks and application in solar-to-vapor conversion. Chinese Journal of Structural Chemistry, 2024, 43(8): 100380-100380. doi: 10.1016/j.cjsc.2024.100380
11. [11]
  Huijie An , Chen Yang , Zhihui Jiang , Junjie Yuan , Zhongming Qiu , Longhao Chen , Xin Chen , Mutu Huang , Linlang Huang , Hongju Lin , Biao Cheng , Hongjiang Liu , Zhiqiang Yu . Luminescence-activated Pt(Ⅳ) prodrug for in situ triggerable cancer therapy. Chinese Chemical Letters, 2024, 35(7): 109134-. doi: 10.1016/j.cclet.2023.109134
12. [12]
  Chaohui Zheng , Jing Xi , Shiyi Long , Tianpei He , Rui Zhao , Xinyuan Luo , Na Chen , Quan Yuan . Persistent luminescence encoding for rapid and accurate oral-derived bacteria identification. Chinese Chemical Letters, 2025, 36(1): 110223-. doi: 10.1016/j.cclet.2024.110223
13. [13]
  Yuanpeng Ye , Longfei Yao , Guofeng Liu . Engineering circularly polarized luminescence through symmetry manipulation in achiral tetraphenylpyrazine structures. Chinese Journal of Structural Chemistry, 2025, 44(2): 100460-100460. doi: 10.1016/j.cjsc.2024.100460
14. [14]
  Shuo Li , Xinran Liu , Yongjie Zheng , Jun Ma , Shijie You , Heshan Zheng . Effective peroxydisulfate activation by CQDs-MnFe₂O₄@ZIF-8 catalyst for complementary degradation of bisphenol A by free radicals and non-radical pathways. Chinese Chemical Letters, 2024, 35(5): 108971-. doi: 10.1016/j.cclet.2023.108971
15. [15]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
16. [16]
  Zhao-Xia Lian , Xue-Zhi Wang , Chuang-Wei Zhou , Jiayu Li , Ming-De Li , Xiao-Ping Zhou , Dan Li . Producing circularly polarized luminescence by radiative energy transfer from achiral metal-organic cage to chiral organic molecules. Chinese Chemical Letters, 2024, 35(8): 109063-. doi: 10.1016/j.cclet.2023.109063
17. [17]
  Yongjing Deng , Feiyang Li , Zijian Zhou , Mengzhu Wang , Yongkang Zhu , Jianwei Zhao , Shujuan Liu , Qiang Zhao . Chiral induction and Sb³⁺ doping in indium halides to trigger second harmonic generation and circularly polarized luminescence. Chinese Chemical Letters, 2024, 35(8): 109085-. doi: 10.1016/j.cclet.2023.109085
18. [18]
  Junying Zhang , Ruochen Li , Haihua Wang , Wenbing Kang , Xing-Dong Xu . Photo-induced tunable luminescence from an aggregated amphiphilic ethylene-pyrene derivative in aqueous media. Chinese Chemical Letters, 2024, 35(6): 109216-. doi: 10.1016/j.cclet.2023.109216
19. [19]
  Hui-Juan Wang , Wen-Wen Xing , Zhen-Hai Yu , Yong-Xue Li , Heng-Yi Zhang , Qilin Yu , Hongjie Zhu , Yao-Yao Wang , Yu Liu . Cucurbit[7]uril confined phenothiazine bridged bis(bromophenyl pyridine) activated NIR luminescence for lysosome imaging. Chinese Chemical Letters, 2024, 35(6): 109183-. doi: 10.1016/j.cclet.2023.109183
20. [20]
  Sifan Du , Yuan Wang , Fulin Wang , Tianyu Wang , Li Zhang , Minghua Liu . Evolution of hollow nanosphere to microtube in the self-assembly of chiral dansyl derivatives and inversed circularly polarized luminescence. Chinese Chemical Letters, 2024, 35(7): 109256-. doi: 10.1016/j.cclet.2023.109256

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(193)
HTML views(7)

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