Abstract
Producing ultra-stabilized radicals via light irradiation has raised considerable concern but remains a tremendous challenge in functional materials. Herein, optically actuating ultra-stable radicals are discovered in a sterically encumbered and large π-conjugated tri(4-pyridyl)-1,3,5-triazine (TPT) ligands constructed photochromic compound Cu3(H-HEDP)2TPT2-2H2O (QDU-12; HEDP=hydroxyethylidene diphosphonate). The photogeneration of TPT• radicals is the photoactive behavior of electron transfer from HEDP motifs to TPT units. The ultra-long-lived radicals are contributed from strong interchain π-π interactions between the large π-conjugated TPT components, with the radical lifetime maintained for about 18 months under ambient conditions. Moreover, the antiferromagnetic couplings between TPT• radicals and Cu2+ ions plummeted the demagnetization to 35% of its original state after light irradiation, showing the largest room temperature photodemagnetization in the current radical-based photochromic materials.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Ratera I, Veciana J. Chem Soc Rev, 2012, 41: 303–349
Zeng Z, Shi X, Chi C, López Navarrete JT, Casado J, Wu J. Chem Soc Rev, 2015, 44: 6578–6596
Zhou J, Zhu W, Zeng M, Yang Q, Li P, Lan L, Peng J, Li Y, Huang F, Cao Y. Sci China Chem, 2019, 62: 1656–1665
Ai X, Evans EW, Dong S, Gillett AJ, Guo H, Chen Y, Hele TJH, Friend RH, Li F. Nature, 2018, 563: 536–540
Chen X, Zhao W, Baryshnikov G, Steigerwald ML, Gu J, Zhou Y, Ågren H, Zou Q, Chen W, Zhu L. Nat Commun, 2020, 11: 945
Wang W, Wang L, Chen S, Yang W, Zhang Z, Wang X. Sci China Chem, 2018, 61: 300–305
Cui Z, Abdurahman A, Ai X, Li F. CCS Chem, 2020, 2: 1129–1145
Hu X, Chen H, Zhao L, Miao M, Zheng Y. Chem Mater, 2019, 31: 10256–10262
Miura T, Maeda K, Oka Y, Ikoma T. J Phys Chem B, 2018, 122: 12173–12183
Tang S, Zhang L, Ruan H, Zhao Y, Wang X. J Am Chem Soc, 2020, 142: 7340–7344
Ji L, Shi J, Wei J, Yu T, Huang W. Adv Mater, 2020, 32: 1908015
Meng X, Shi W, Cheng P. Coord Chem Rev, 2019, 378: 134–150
Wang Y, Hickox HP, Xie Y, Wei P, Blair SA, Johnson MK, Schaefer Iii HF, Robinson GH. J Am Chem Soc, 2017, 139: 6859–6862
Cobo S, Ostrovskii D, Bonhommeau S, Vendier L, Molnar G, Salmon L, Tanaka K, Bousseksou A. J Am Chem Soc, 2008, 130: 9019–9024
Meng YS, Liu T. Acc Chem Res, 2019, 52: 1369–1379
Zak JK, Miyasaka M, Rajca S, Lapkowski M, Rajca A. J Am Chem Soc, 2010, 132: 3246–3247
Kato K, Osuka A. Angew Chem Int Ed, 2019, 58: 8978–8986
Wu J, Tao C, Li Y, Li J, Yu J. Chem Sci, 2015, 6: 2922–2927
Gao CY, Yang Y, Ai J, Tian HR, Li LJ, Yang W, Dang S, Sun ZM. Chem Eur J, 2016, 22: 11652–11659
Shen JJ, Li XX, Yu TL, Wang F, Hao PF, Fu YL. Inorg Chem, 2016, 55: 8271–8273
Li L, Wang JR, Hua Y, Guo Y, Fu C, Sun YN, Zhang H. J Mater Chem C, 2019, 7: 38–42
Ma YJ, Hu JX, Han SD, Pan J, Li JH, Wang GM. J Am Chem Soc, 2020, 142: 2682–2689
Li SL, Han M, Zhang Y, Li GP, Li M, He G, Zhang XM. J Am Chem Soc, 2019, 141: 12663–12672
Yu XQ, Sun C, Liu BW, Wang MS, Guo GC. Nat Commun, 2020, 11: 1179
Mallick A, Garai B, Addicoat MA, Petkov PS, Heine T, Banerjee R. Chem Sci, 2015, 6: 1420–1425
Bonanno NM, Lough AJ, Lemaire MT. Inorg Chem, 2018, 57: 4837–4840
Cheng L, Zhao JW, Yang GY. Dalton Trans, 2014, 43: 7324–7330
Jiao CQ, Zhao Z, Ma C, Sun ZG, Dong DP, Zhu YY, Li J. Cryst Growth Des, 2016, 16: 5624–5635
Dessapt R, Collet M, Coue V, Bujoli-Doeuff M, Jobic S, Lee C, Whangbo MH. Inorg Chem, 2009, 48: 574–580
Ma P, Hu F, Wan R, Huo Y, Zhang D, Niu J, Wang J. J Mater Chem C, 2016, 4: 5424–5433
Sun JK, Yang XD, Yang GY, Zhang J. Coord Chem Rev, 2019, 378: 533–560
Zhang CJ, Chen ZW, Lin RG, Zhang MJ, Li PX, Wang MS, Guo GC. Inorg Chem, 2014, 53: 847–851
Kavarnos GJ, Turro NJ. Chem Rev, 1986, 86: 401–449
Matsuda K, Takayama K, Irie M. Inorg Chem, 2004, 43: 482–489
Liu J. Dyes Pigments, 2019, 160: 476–482
Li SL, Li M, Zhang Y, Xu HM, Zhang XM. Inorg Chem, 2020, 59: 9047–9054
Ma YJ, Han SD, Pan J, Mu Y, Li JH, Wang GM. J Mater Chem C, 2018, 6: 9341–9344
Gong T, Li P, Sui Q, Zhou LJ, Yang NN, Gao EQ. Inorg Chem, 2018, 57: 6791–6794
Ma YJ, Hu JX, Han SD, Pan J, Li JH, Wang GM. Chem Commun, 2019, 55: 5631–5634
Xia B, Zhou Y, Wang QL, Xu XF, Tong YZ, Bu XH, Li JR. Dalton Trans, 2018, 47: 15888–15896
Gong T, Yang X, Sui Q, Qi Y, Xi FG, Gao EQ. Inorg Chem, 2016, 55: 96–103
Wang J, Li SL, Zhang XM. ACS Appl Mater Interfaces, 2016, 8: 24862–24869
Jin XH, Wang J, Sun JK, Zhang HX, Zhang J. Angew Chem Int Ed, 2011, 50: 1149–1153
Jiang W, Jiao C, Meng Y, Zhao L, Liu Q, Liu T. Chem Sci, 2018, 9: 617–622
Zhang N, Han Y, Du M, Sa R, Wang M, Guo G. Chem Eur J, 2019, 25: 13972–13976
Cai LZ, Jiang XM, Zhang ZJ, Guo PY, Jin AP, Wang MS, Guo GC. Inorg Chem, 2017, 56: 1036–1040
Yin P, Zheng LM, Gao S, Xin XQ. Chem Commun, 2001, 37: 2346–2347
Cai LZ, Chen QS, Zhang CJ, Li PX, Wang MS, Guo GC. J Am Chem Soc, 2015, 137: 10882–10885
Acknowledgements
This work was supported by the National Natural Science Foundation of China (21901133, 22071125, 22071126, 21571111) and the Key Research and Development Project of Shandong Province (2019GGX102006). We thank for Dr Jian-Hua Qin (Luoyang Normal University, China) for the SCXRD data refinements.
Author information
Authors and Affiliations
Corresponding author
Additional information
Conflict of interest
The authors declare no conflict of interest.
Supporting Information
Rights and permissions
About this article
Cite this article
Hu, JX., Jiang, XF., Ma, YJ. et al. Optically actuating ultra-stable radicals in a large π-conjugated ligand constructed photochromic complex. Sci. China Chem. 64, 432–438 (2021). https://doi.org/10.1007/s11426-020-9891-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-020-9891-4