How the Length of Through‐Space Conjugation Influences the Clusteroluminescence of Oligo(Phenylene Methylene)s

Author:

Wang Lei12ORCID,Xiong Zuping123ORCID,Zhi Sun Jing13ORCID,Huang Feihe24ORCID,Zhang Haoke123ORCID,Zhong Tang Ben15ORCID

Affiliation:

1. MOE Key Laboratory of Macromolecular Synthesis and Functionalization Department of Polymer Science and Engineering Zhejiang University Hangzhou 310058 China

2. Zhejiang-Israel Joint Laboratory of Self-Assembling Functional Materials ZJU-Hangzhou Global Scientific and Technological Innovation Center Zhejiang University Hangzhou 311215 China

3. Centre of Healthcare Materials Shaoxing Institute Zhejiang University Shaoxing 312000 China

4. Stoddart Institute of Molecular Science Department of Chemistry Zhejiang University Hangzhou 310058 China

5. School of Science and Engineering Shenzhen Institute of Aggregate Science and Technology The Chinese University of Hong Kong, Shenzhen (CUHK-Shenzhen) Guangdong 518172 China

Abstract

AbstractThe length and mode of conjugation directly affect the molecular electronic structure, which has been extensively studied in through‐bond conjugation (TBC) systems. Corresponding research greatly promotes the development of TBC‐based luminophores. However, how the length and mode of through‐space conjugation (TSC), one kind of weak interaction, influence the photophysical properties of non‐conjugated luminophores remains a relatively unexplored field. Here, we unveil a non‐linear relationship between TSC length and emission characteristics in non‐conjugated systems, in contrast to the reported proportional correlation in TBC systems. More specifically, oligo(phenylene methylene)s (OPM[4]‐OPM[7]) exhibit stronger TSC and prominent blue clusteroluminescence (CL) (≈440 nm) compared to shorter counterparts (OPM[2] and OPM[3]). OPM[6] demonstrates the highest solid‐state quantum yield (40 %), emphasizing the importance of balancing flexibility and rigidity. Further theoretical calculations confirmed that CL of these oligo(phenylene methylene)s was determined by stable TSC derived from the inner rigid Diphenylmethane (DPM) segments within the oligomers instead of the outer ones. This discovery challenges previous assumptions and adds a new dimension to the understanding of TSC‐based luminophores in non‐conjugated systems.

Funder

National Natural Science Foundation of China

China Postdoctoral Science Foundation

Publisher

Wiley

Subject

General Medicine

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