Excited-State Odd-Even Effect in Through-Space Interactions

Zuping Xiong; Jianyu Zhang; Jing Zhi Sun; Haoke Zhang; Ben Zhong Tang

doi:10.1021/jacs.3c08164

Excited-State Odd-Even Effect in Through-Space Interactions

J Am Chem Soc. 2023 Sep 27;145(38):21104-21113. doi: 10.1021/jacs.3c08164. Epub 2023 Sep 15.

Authors

Zuping Xiong^{1

2

3}, Jianyu Zhang⁴, Jing Zhi Sun^{1

3}, Haoke Zhang^{1

2

3}, Ben Zhong Tang^{1

4

5}

Affiliations

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 Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology, Hong Kong 999077, China.
⁵ School of Science and Engineering, Shenzhen Institute of Aggregate Science and Technology, The Chinese University of Hong Kong, Shenzhen (CUHK-Shenzhen), Guangzhou 518172, China.

PMID: 37715315
DOI: 10.1021/jacs.3c08164

Abstract

The odd-even effect is a fantastic phenomenon in nature, which has been applied in diverse fields such as organic self-assembled monolayers and liquid crystals. Currently, the origin of each odd-even effect remains elusive, and all of the reported odd-even effects are related to the ground-state properties. Here, we discover an excited-state odd-even effect in the through-space interaction (TSI) of nonconjugated tetraphenylalkanes (TPAs). The TPAs with an even number of alkyl carbon atoms (C2-TPA, C4-TPA, and C6-TPA) show strong TSI, long-wavelength emission, and high QY. However, the odd ones (C1-TPA, C3-TPA, C5-TPA, and C7-TPA) are almost nonexistent with negligible QY. Systematically experimental and theoretical results reveal that the excited-state odd-even effect is synthetically determined by three factors: alkyl geometry, molecular movability, and intermolecular packing. Moreover, these flexible luminescent TPAs possess tremendous advantages in fluorescent information encryptions. This work extends the odd-even effect to photophysics, demonstrating its substantial importance and universality in nature.