Synergistic effects of triplet–triplet annihilation and reverse intersystem crossing in a platinum-based electrochemiluminescent metallopolymer emitter

Chun Hong Mak; Yaojia Ai; Chunyan Tan; Wenxin Niu; Kuan-Chen Cheng; Chang-Wei Hsieh; Hsin-Hui Shen; Zheng Hu; Yanqing Tian; Xueqing Xu; Guizheng Zou; Duu-Jong Lee; Hsien-Yi Hsu

doi:10.1039/D4TC05445H

Synergistic effects of triplet–triplet annihilation and reverse intersystem crossing in a platinum-based electrochemiluminescent metallopolymer emitter†

Chun Hong Mak,

^ab Yaojia Ai,

^e Chunyan Tan,

^d Wenxin Niu,^g Kuan-Chen Cheng,^hijkq Chang-Wei Hsieh,

^lrs Hsin-Hui Shen,^m Zheng Hu,

ⁿ Yanqing Tian,

^o Xueqing Xu,

^p Guizheng Zou,

*^e Duu-Jong Lee*^b and Hsien-Yi Hsu

*^acf

Author affiliations

* Corresponding authors

^a School of Energy and Environment, City University of Hong Kong, Kowloon Tong, Hong Kong, China
E-mail: sam.hyhsu@cityu.edu.hk

^b Department of Mechanical Engineering, City University of Hong Kong, Kowloon Tong, Hong Kong, China
E-mail: tuclee@cityu.edu.hk

^c Department of Materials Science and Engineering, Centre for Functional Photonics (CFP), City University of Hong Kong, Kowloon Tong, Hong Kong, China

^d The State Key Laboratory of Chemical Oncogenomics, the Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, P. R. China

^e School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China
E-mail: zouguizheng@sdu.edu.cn

^f Shenzhen Research Institute of City University of Hong Kong, Shenzhen 518057, P. R. China

^g State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun, Jilin 130022, P. R. China

^h Department of Optometry, Asia University, 500, Lioufeng Rd., Wufeng, Taichung, Taiwan

ⁱ Institute of Food Science and Technology, National Taiwan University, No. 1, Sec. 4, Roosevelt Rd., Taipei 10617, Taiwan

^j Department of Medical Research, China Medical University Hospital, China Medical University, 91, Hsueh-Shih Road, Taichung, Taiwan

^k Institute of Biotechnology, National Taiwan University, No. 1, Sec. 4, Roosevelt Rd., Taipei 10617, Taiwan

^l Department of Food Science and Biotechnology, National Chung Hsing University, 145 Xingda Rd., South Dist., Taichung City, Taiwan

^m Department of Materials Science and Engineering, Faculty of Engineering, Monash University, Clayton, Victoria 3800, Australia

ⁿ Key Laboratory of Mesoscopic Chemistry of MOE and Jiangsu Provincial Laboratory for Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China

^o Department of Materials Science and Engineering, Southern University of Science and Technology, Xili, Nanshan District, Shenzhen 518055, China

^p Key Laboratory of Renewable Energy, Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, P. R. China

^q Dept of Food Science, Fu Jen Catholic University, 24205, New Taipei City, Taiwan

^r Department of Food Science, National Ilan University, Shennong Road, Yilan City 26047, Taiwan

^s Department of Medical Research, China Medical University Hospital, Taichung City, Taiwan

Abstract

This work presents the synthesis, electrochemical behavior, and photophysical properties of a novel platinum acetylide metallopolymer (p-PtBTD), designed for enhanced electrogenerated chemiluminescence (ECL) performance. The metallopolymer features alternating π-conjugated segments of 2,1,3-benzothiadiazole (BTD) and trans-Pt(PBu₃)₂ units. The inclusion of platinum centers facilitates efficient intersystem crossing (ISC), allowing the radiative decay of triplet excitons, which is typically challenging in conventional ECL systems dominated by singlet emission. Photoluminescence (PL) studies reveal dual emission, with a prominent fluorescence peak at 584 nm and a weak phosphorescence peak near 800 nm. Electrochemical investigations demonstrate quasi-reversible oxidation and irreversible reduction waves for p-PtBTD, while transient ECL studies reveal instability in the radical cation, which has been successfully addressed using tripropylamine (TPrA) as a co-reactant. The ECL spectrum shows dual emission arising from both singlet and triplet states, facilitated by triplet–triplet annihilation (TTA) and reverse intersystem crossing (RISC) due to a small energy gap (∼0.5 eV) between these states. This dual emission mechanism, involving both fluorescence and phosphorescence, highlights the potential of p-PtBTD for advanced ECL applications, particularly in sensing and optoelectronics. These findings underscore the utility of metallopolymers in overcoming the limitations of traditional ECL systems, paving the way for more efficient and versatile luminescent materials.

Journal of Materials Chemistry C

Synergistic effects of triplet–triplet annihilation and reverse intersystem crossing in a platinum-based electrochemiluminescent metallopolymer emitter†

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Synergistic effects of triplet–triplet annihilation and reverse intersystem crossing in a platinum-based electrochemiluminescent metallopolymer emitter

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