Citation: Pei WANG, Chun-Hua HUANG, Xu-Lin CHEN, Can-Zhong LU. A Tetranuclear Cuprous Halide Cluster Exhibiting Efficient Blue Thermally Activated Delayed Fluorescence[J]. Chinese Journal of Structural Chemistry, ;2021, 40(11): 1489-1495. doi: 10.14102/j.cnki.0254-5861.2011-3197 shu

A Tetranuclear Cuprous Halide Cluster Exhibiting Efficient Blue Thermally Activated Delayed Fluorescence

Pei WANG ^{a, b, e} ,
Chun-Hua HUANG ^{b, c, d} ,
Xu-Lin CHEN ^{a, b, c} ,
Can-Zhong LU ^{a, b, e,,}

a.
CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
b.
Xiamen Institute of Rare-earth Materials Haixi Institutes, Chinese Academy of Sciences, Xiamen 361021, China
c.
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, China
d.
Huaqiao University, Xiamen 361021, China
e.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Can-Zhong LU, czlu@fjirsm.ac.cn
Received Date: 26 March 2021
Accepted Date: 13 May 2021

Fund Project: the Strategic Priority Research Program of the Chinese Academy of Sciences XDB20000000the Key Research Program of Frontier Science, CAS QYZDJ-SSW-SLH033the National Natural Science Foundation of China 52073286the National Natural Science Foundation of China 21805281the National Natural Science Foundation of China 21875252the Natural Science Foundation of Fujian Province 2006L2005the Natural Science Foundation of Fujian Province 2019J01125the Youth Innovation Foundation of Xiamen City 3502Z20206082the Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China 2021ZR132

Figures(6)

A new tetranuclear cuprous halide complex, (CuBr)₄(PN)₂ (PN = 2-(diphenylphosphaneyl)-6-methoxypyridine), was synthesized and fully characterized. In solid state, this complex exhibits efficient blue emission with a photoluminescence quantum yield of 43.3% and a decay time of 19 μs at room temperature. The theoretical calculations, combined with the temperature dependence of spectroscopic properties and emission decay behaviors, indicate that the emission in the solid state originates from the ^{1, 3}(MLCT + XLCT) excited states, which are in thermal equilibrium with a small energy gap of about 0.1 eV.
- cuprous complex,
- thermally activated delayed fluorescence,
- blue emission,
- photoluminescence
1. [1]
  Mahoro, G. U.; Fernandez-Cestau, J.; Renaud, J. L.; Coto, P. B.; Costa, R. D.; Gaillard, S. Recent advances in solid-state lighting devices using transition metal complexes exhibiting thermally activated delayed fluorescent emission mechanism. Adv. Opt. Mater. 2020, 8.
2. [2]
  Cao, L.; Huang, S.; Liu, W.; Zhao, H.; Xiong, X. G.; Zhang, J. P.; Fu, L. M.; Yan, X. Thermally activated delayed fluorescence from d(10)-metal carbene complexes through intermolecular charge transfer and multicolor emission with a monomer-dimer equilibrium. Chem. Eur. J. 2020, 26, 17222–17229. doi: 10.1002/chem.202004106
3. [3]
  Lin, L.; Chen, D. H.; Yu, R.; Chen, X. L.; Zhu, W. J.; Liang, D.; Chang, J. F.; Zhang, Q.; Lu, C. Z. Photo- and electro-luminescence of three tadf binuclear Cu(Ⅰ) complexes with functional tetraimine ligands. J. Mater. Chem. C 2017, 5, 4495–4504. doi: 10.1039/C7TC00443E
4. [4]
  Liang, D.; Chen, X. L.; Liao, J. Z.; Hu, J. Y.; Jia, J. H.; Lu, C. Z. Highly efficient cuprous complexes with thermally activated delayed fluorescence for solution-processed organic light-emitting devices. Inorg. Chem. 2016, 55, 7467–7475. doi: 10.1021/acs.inorgchem.6b00763
5. [5]
  Yersin, H.; Czerwieniec, R.; Shafikov, M. Z.; Suleymanova, A. F. Tadf material design: photophysical background and case studies focusing on Cu(Ⅰ) and Ag(Ⅰ) complexes. ChemPhysChem. 2017, 18, 3508–3535. doi: 10.1002/cphc.201700872
6. [6]
  Chen, X. L.; Yu, R.; Zhang, Q. K.; Zhou, L. J.; Wu, X. Y.; Zhang, Q.; Lu, C. Z. Rational design of strongly blue-emitting cuprous complexes with thermally activated delayed fluorescence and application in solution-processed oleds. Chem. Mater. 2013, 25, 3910–3920. doi: 10.1021/cm4024309
7. [7]
  Chen, X. L.; Yu, R.; Wu, X. Y.; Liang, D.; Jia, J. H.; Lu, C. Z. A strongly greenish-blue-emitting Cu₄Cl₄ cluster with an efficient spin-orbit coupling (soc): fast phosphorescence versus thermally activated delayed fluorescence. Chem. Commun. 2016, 52, 6288–6291. doi: 10.1039/C6CC00809G
8. [8]
  Egly, J.; Bissessar, D.; Achard, T.; Heinrich, B.; Steffanut, P.; Mauro, M.; Bellemin-Laponnaz, S. Copper(Ⅰ) complexes with remotely functionalized phosphine ligands: synthesis, structural variety, photophysics and effect onto the optical properties. Inorg. Chim. Acta 2021, 514.
9. [9]
  Sun, C.; Guo, Y. H.; Han, S. S.; Li, J. Z.; Jiang, K.; Dong, L. F.; Liu, Q. L.; Yue, C. Y.; Lei, X. W. Three-dimensional cuprous lead bromide framework with highly efficient and stable blue photoluminescence emission. Angew. Chem., Int. Ed. 2020, 59, 16465–16469. doi: 10.1002/anie.202006990
10. [10]
  Calvo, M.; Crespo, O.; Gimeno, M. C.; Laguna, A.; Olivan, M. T.; Polo, V.; Rodriguez, D.; Saez-Rocher, J. M. Tunable from blue to red emissive composites and solids of silver diphosphane systems with higher quantum yields than the diphosphane ligands. Inorg. Chem. 2020, 59, 14447–14456. doi: 10.1021/acs.inorgchem.0c02238
11. [11]
  Hofbeck, T.; Monkowius, U.; Yersin, H. Highly efficient luminescence of Cu(Ⅰ) compounds: thermally activated delayed fluorescence combined with short-lived phosphorescence. J. Am. Chem. Soc. 2015, 137, 399–404. doi: 10.1021/ja5109672
12. [12]
  Gan, X. M.; Yu, R.; Chen, X. L.; Yang, M.; Lin, L.; Wu, X. Y.; Lu, C. Z. A unique tetranuclear Ag(Ⅰ) complex emitting efficient thermally activated delayed fluorescence with a remarkably short decay time. Dalton Trans. 2018, 47, 5956–5960. doi: 10.1039/C8DT00837J
13. [13]
  Frisch, M. J. T.; G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H. C.; M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R. H.; J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A. Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. H., J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J.; C.; Iyengar, S. S. T. J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R. S., 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. S. P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT. Gaussian 09, Revision D. 01 2009.
14. [14]
  Lu, T.; Chen, F. W. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 2012, 33, 580–592. doi: 10.1002/jcc.22885
15. [15]
  Chen, X. L.; Lin, C. S.; Wu, X. Y.; Yu, R.; Teng, T.; Zhang, Q. K.; Zhang, Q.; Yang, W. B.; Lu, C. Z. Highly efficient cuprous complexes with thermally activated delayed fluorescence and simplified solution process oleds using the ligand as host. J. Mater. Chem. C 2015, 3, 1187–1195. doi: 10.1039/C4TC02255F
16. [16]
  Jia, J. H.; Chen, X. L.; Liao, J. Z.; Liang, D.; Yang, M. X.; Yu, R.; Lu, C. Z. Highly luminescent copper(Ⅰ) halide complexes chelated with a tetradentate ligand (pnnp): synthesis, structure, photophysical properties and theoretical studies. Dalton Trans. 2019, 48, 1418–1426. doi: 10.1039/C8DT03452D
17. [17]
  Zhang, D.; Song, X.; Gillett, A. J.; Drummond, B. H.; Jones, S. T. E.; Li, G.; He, H.; Cai, M.; Credgington, D.; Duan, L. Efficient and stable deep-blue fluorescent organic light-emitting diodes employing a sensitizer with fast triplet upconversion. Adv. Mater. 2020, 32, e1908355. doi: 10.1002/adma.201908355
18. [18]
  Chen, X. L.; Jia, J. H.; Yu, R.; Liao, J. Z.; Yang, M. X.; Lu, C. Z. Combining charge-transfer pathways to achieve unique thermally activated delayed fluorescence emitters for high-performance solution-processed, non-doped blue oleds. Angew. Chem., Int. Ed. 2017, 56, 15006–15009. doi: 10.1002/anie.201709125
1. [1]
  Zhengkun QIN , Lixin BAO , Yunkai ZHANG , Lin CUI , Jinyu WANG , Yuhao WANG , Mingxing SONG . Theoretical study on the thermally activated delayed fluorescence, and efficiency roll-off characteristics of a series of blue and blue-green Ir(Ⅲ) complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(2): 365-374. doi: 10.11862/CJIC.20250222
2. [2]
  Zheng Zhao , Ben Zhong Tang . An efficient strategy enabling solution processable thermally activated delayed fluorescence emitter with high horizontal dipole orientation. Chinese Journal of Structural Chemistry, 2024, 43(6): 100270-100270. doi: 10.1016/j.cjsc.2024.100270
3. [3]
  Ming ZHENG , Yixiao ZHANG , Jian YANG , Pengfei GUAN , Xiudong LI . Energy storage and photoluminescence properties of Sm³⁺-doped Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ lead-free multifunctional ferroelectric ceramics. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 686-692. doi: 10.11862/CJIC.20230388
4. [4]
  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
5. [5]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
6. [6]
  Yanting HUANG , Hua XIANG , Mei PAN . Construction and application of multi-component systems based on luminous copper nanoclusters. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2075-2090. doi: 10.11862/CJIC.20240196
7. [7]
  Liwen Wang , Boyang Wang , Siyu Lu , Shubo Lv , Xiaoli Qu . High quantum yield yellow emission carbon dots for the construction of blue light blocking films. Chinese Chemical Letters, 2025, 36(2): 110497-. doi: 10.1016/j.cclet.2024.110497
8. [8]
  Xiaoqin Du , Peiyao Pan , Haoqi Li , Di Zhang , Wentao Huang , Xi Kang , Manzhou Zhu . Assessing the photoluminescence of metal nanoclusters: The individual versus the collective. Chinese Chemical Letters, 2026, 37(2): 111155-. doi: 10.1016/j.cclet.2025.111155
9. [9]
  Fan Yang , Guan , Huang Zhang , Hai-Ling Wang , Wen-Wen Qin , Zhong-Hong Zhu , Fu-Pei Liang , Hua-Hong Zou . Ultrasonic cutting strategy yields lanthanide organic nanochains with bright emission: thermally enhanced luminescence and bio-optical imaging. Chinese Journal of Structural Chemistry, 2026, 45(1): 100761-100761. doi: 10.1016/j.cjsc.2025.100761
10. [10]
  Junxiu Zhao , Jingya Shi , Xiaoli Sun , Siyu Wang , Xuwei Han , Xiaoni Zhao , Jisheng Nie , Yongkang Yue . Heptamethine cyanine with 1239 nm fluorescence emission for in vivo imaging. Chinese Chemical Letters, 2026, 37(4): 111317-. doi: 10.1016/j.cclet.2025.111317
11. [11]
  Hang Meng , Bicheng Zhu , Ruolun Sun , Zixuan Liu , Shaowen Cao , Kan Zhang , Jiaguo Yu , Jingsan Xu . Dynamic photoluminescence switching of carbon nitride thin films for anticounterfeiting and encryption. Chinese Journal of Structural Chemistry, 2024, 43(10): 100410-100410. doi: 10.1016/j.cjsc.2024.100410
12. [12]
  Ping Wang , Chunmao Chen , Hongwei Ren , Erhong Duan . A review of carbon dots in synthesis strategies, photoluminescence mechanisms, and applications in wastewater treatment. Chinese Chemical Letters, 2025, 36(9): 110725-. doi: 10.1016/j.cclet.2024.110725
13. [13]
  Zhi-Long Li , Hao-Fei Ni , Bo Zhuang , Kun Ding , Da-Wei Fu , Qiang Guo , Meng-Meng Lun . Halogen substitution strategy for regulating the photoluminescence and dielectric response of ferroelastics. Chinese Chemical Letters, 2026, 37(4): 110755-. doi: 10.1016/j.cclet.2024.110755
14. [14]
  Rong Zhang , Yong Chen , Zhiyi Yu , Yu Liu . Laponite cascade assembly activated reversible multicolor luminescence supramolecular hydrogel with near-infrared emission. Chinese Chemical Letters, 2026, 37(1): 111147-. doi: 10.1016/j.cclet.2025.111147
15. [15]
  Lulu DONG , Jie LIU , Hua YANG , Yupei FU , Hongli LIU , Xiaoli CHEN , Huali CUI , Lin LIU , Jijiang WANG . Synthesis, crystal structure, and fluorescence properties of Cd-based complex with pcu topology. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 809-820. doi: 10.11862/CJIC.20240171
16. [16]
  Linnan Jiang , Zhenkai Qian , Yong Chen , Xiaoyong Yu , Yugui Qiu , Wen-Wen Xu , Yonghui Sun , Xiufang Xu , Lihua Wang , Yu Liu . Double response reversible phosphorescence based on cyclodextrin supramolecular flexible elastic achieved multicolor delayed fluorescence. Chinese Chemical Letters, 2025, 36(8): 110676-. doi: 10.1016/j.cclet.2024.110676
17. [17]
  Yiqiao Chen , Ao Liu , Biwen Yang , Zhenzhen Li , Binggang Ye , Zhouyi Guo , Zhiming Liu , Haolin Chen . Photoluminescence and photothermal conversion in boric acid derived carbon dots for targeted microbial theranostics. Chinese Chemical Letters, 2024, 35(9): 109295-. doi: 10.1016/j.cclet.2023.109295
18. [18]
  Tiantian Gong , Yanan Chen , Shuo Wang , Miao Wang , Junwei Zhao . Rigid-flexible-ligand-ornamented lanthanide-incorporated selenotungstates and photoluminescence properties. Chinese Journal of Structural Chemistry, 2024, 43(9): 100370-100370. doi: 10.1016/j.cjsc.2024.100370
19. [19]
  Huan Hu , Ying Zhang , Shi-Shuang Huang , Zhi-Gang Li , Yungui Liu , Rui Feng , Wei Li . Temperature- and pressure-responsive photoluminescence in a 1D hybrid lead halide. Chinese Journal of Structural Chemistry, 2024, 43(10): 100395-100395. doi: 10.1016/j.cjsc.2024.100395
20. [20]
  Peipei CUI , Xin LI , Yilin CHEN , Zhilin CHENG , Feiyan GAO , Xu GUO , Wenning YAN , Yuchen DENG . Transition metal coordination polymers with flexible dicarboxylate ligand: Synthesis, characterization, and photoluminescence property. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2221-2231. doi: 10.11862/CJIC.20240234

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(1161)
HTML views(22)

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