Citation: Jianfang Cao, Xue Ma, Xinyu Chen, Tianci Zhang, Wen Sun. Theoretical perspective on fine-tuning ISC efficiency in D-A BODIPY photosensitizers through heteroatom incorporation and nitrogen ring strain modulation[J]. Chinese Chemical Letters, ;2025, 36(10): 110897. doi: 10.1016/j.cclet.2025.110897 shu

Theoretical perspective on fine-tuning ISC efficiency in D-A BODIPY photosensitizers through heteroatom incorporation and nitrogen ring strain modulation

Jianfang Cao ^{a, *,} ,
Xue Ma ^a ,
Xinyu Chen ^a ,
Tianci Zhang ^a ,
Wen Sun ^{b, *,}

a.
School of Chemical Engineering, Ocean and Life Sciences, Dalian University of Technology, Panjin Campus, Panjin 124221, China
b.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, High-tech District, Dalian 116024, China

caojf@dlut.edu.cn

sunwen@dlut.edu.cn

Received Date: 10 November 2024
Revised Date: 12 January 2025
Accepted Date: 20 January 2025
Available Online: 21 January 2025

Figures(4)

This study investigates the intersystem crossing (ISC) mechanism in donor-acceptor (D-A) type distyryl-BODIPY photosensitizers, including previously reported M1 (benzene donor), M2, M3 (phenothiazine donors), and newly predicted M4 (triphenylamine donor), M5-M7 (nitrogen-containing aliphatic rings with thiophene donors). Using computational chemistry, we analyzed their geometric configurations, spectral properties, spin-orbit coupling, and electron-hole orbitals. We found that S₂ is a charge transfer singlet state (¹CT), T₂ is a locally excited triplet state (³LE), and the S₂ → T₂ transition is the main ISC pathway in M2-M7, following the ¹CT → ³LE mechanism. M5-M7 show near-vertical dihedral angles between donor and acceptor in the S₂ state relative to M2-M4, facilitating charge transfer. The strain energies in the nitrogen-containing rings of M5-M7 affect oxidation potentials and ISC. M5, with the highest strain energy, shows the lowest oxidation potential, smaller ΔE_S2-T2, highest SOC, and fastest k_isc, making it the most efficient predicted singlet oxygen producer. This research clarifies the structure-performance relationships of near-infrared D-A type distyryl-BODIPY photosensitizers and provides a theoretical foundation for developing heavy-atom-free photosensitizers with tuned fluorescence quantum yield and singlet oxygen quantum yield.
1. [1]
  N.R. Datta, S. Gómez Ordóñez, U.S. Gaipl, et al., Cancer Treat. Rev. 41 (2015) 742-753. doi: 10.1016/j.ctrv.2015.05.009
2. [2]
  J. Wang, Q.B. Gong, L.J. Jiao, E.H. Hao, Coord. Chem. Rev. 496 (2023) 215367. doi: 10.1016/j.ccr.2023.215367
3. [3]
  W.Q. Jiang, M.K. Liang, Q.F. Lei, G.Z. Li, S. Wu, Cancers 15 (2023) 585. doi: 10.3390/cancers15030585
4. [4]
  K.X. Teng, W.K. Chen, L.Y. Niu, et al., Angew. Chem. Int. Ed. 60 (2021) 19912-19920. doi: 10.1002/anie.202106748
5. [5]
  K.K. Wen, H. Tan, Q. Peng, et al., Adv. Mater. 34 (2022) 2108146. doi: 10.1002/adma.202108146
6. [6]
  R. Wang, M.M. He, Z.W. Zhang, et al., Smart Mol. 2 (2024) e20240010. doi: 10.1002/smo.20240010
7. [7]
  J.F. Cao, T.C. Zhang, W. Sun, Dyes Pigm. 208 (2023) 110797. doi: 10.1016/j.dyepig.2022.110797
8. [8]
  H. Gu, W. Sun, J.J. Du, J.L. Fan, X.J. Peng, Smart Mol. 2 (2024) e20230014. doi: 10.1002/smo.20230014
9. [9]
  B. Lu, J.C. Xia, H. Quan, et al., Small 20 (2024) 2307664. doi: 10.1002/smll.202307664
10. [10]
  V.N. Nguyen, Y.B. Yim, S.G. Kim, et al., Angew. Chem. Int. Ed. 59 (2020) 8957-8962. doi: 10.1002/anie.202002843
11. [11]
  L.W. Zhang, S.D. Liu, X. Zhang, J.Y. Sun, L.X. Chen, Smart Mol. 2 (2024) e20230022. doi: 10.1002/smo.20230022
12. [12]
  Y.Q. Hu, Y.Q. Hou, Z.J. Wang, Y.Q. Li, J.Z. Zhao, J. Chem. Phys. 153 (2020) 224304. doi: 10.1063/5.0025224
13. [13]
  Y.T. Gao, X.X. Wang, X.W. He, et al., Adv. Funct. Mater. 29 (2019) 1902673. doi: 10.1002/adfm.201902673
14. [14]
  L.F. Wang, Y. Qian, Biomater. Sci. 11 (2023) 1459-1469. doi: 10.1039/d2bm01838a
15. [15]
  Y.Q. Hou, X. Zhang, K.P. Chen, et al., J. Mater. Chem. C 7 (2019) 12048-12074. doi: 10.1039/c9tc04285g
16. [16]
  J. Deckers, T. Cardeynaels, H. Penxten, et al., Chem. Eur. J. 26 (2020) 15212-15225. doi: 10.1002/chem.202002549
17. [17]
  J. Deckers, T. Cardeynaels, S. Doria, et al., J. Mater. Chem. C 10 (2022) 9344-9355. doi: 10.1039/d2tc01526a
18. [18]
  Y.Q. Hou, Q.Y. Liu, J.Z. Zhao, Chem. Commun. 56 (2020) 1721-1724. doi: 10.1039/c9cc09058d
19. [19]
  Y. Dong, A. Elmali, J.Z. Zhao, B. Dick, A. Karatay, ChemPhysChem 21 (2020) 1388-1401. doi: 10.1002/cphc.202000300
20. [20]
  J.F. Cao, X.Y. Chen, X. Ma, T.C. Zhang, W. Sun, Phys. Chem. Chem. Phys. 26 (2024) 21520-21529. doi: 10.1039/d4cp01346h
21. [21]
  L.J. Ma, Y.J. Geng, G.Y. Zhang, et al., Adv. Health. Mater. 12 (2023) 2300733. doi: 10.1002/adhm.202300733
22. [22]
  T. Lu, Z.Y. Liu, Q.X. Chen, Chin. Phys. B 31 (2022) 126101. doi: 10.1088/1674-1056/ac873a
23. [23]
  S.R. Zhou, R.P. Li, Y. Li, Y.X. Wang, L.H. Feng, J. Mater. Chem. B 10 (2022) 8003-8012. doi: 10.1039/d2tb01578a
24. [24]
  Y. Chen, S. Zhang, T.J. Cheng, et al., J. Mater. Sci. Technol. 141 (2023) 135-148. doi: 10.3847/1538-4357/acd753
25. [25]
  P.H. Xiao, Z.P. Shen, D.L. Wang, et al., Adv. Sci. 9 (2022) 2104079. doi: 10.1002/advs.202104079
26. [26]
  D. Sasikumar, A.T. John, J. Sunny, M. Hariharan, Chem. Soc. Rev. 49 (2020) 6122-6140. doi: 10.1039/d0cs00484g
27. [27]
  X.F. Zhang, N. Feng, Chem. Asian J. 12 (2017) 2447-2456. doi: 10.1002/asia.201700794
28. [28]
  J.F. Cao, T.C. Zhang, X.Y. Chen, X. Ma, J.L. Fan, Smart Mol. 3 (2025) e20240023. doi: 10.1002/smo.20240023
29. [29]
  K. Shizu, H. Tanaka, M. Uejima, et al., J. Phys. Chem. C 119 (2015) 1291-1297. doi: 10.1021/jp511061t
30. [30]
  T. Lu, J. Chem. Phys. 161 (2024) 082503. doi: 10.1063/5.0216272
31. [31]
  Z.Y. Liu, T. Lu, Q.X. Chen, Carbon 165 (2020) 461-467. doi: 10.1016/j.carbon.2020.05.023
32. [32]
  T. Lu, F.W. Chen, J. Comput. Chem. 33 (2012) 580-592. doi: 10.1002/jcc.22885
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2. [2]
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