Two Consecutive Pathways Competing for Supramolecular Polymerization of Naphthalene-diimide Molecules

Yun Huang; Ruilong Zhang; Chengyu Shi; Cong Wang; Rui Liao; Chongwen Zou; Feng Wang; Ningdong Huang

doi:10.1002/chem.202500120

Two Consecutive Pathways Competing for Supramolecular Polymerization of Naphthalene-diimide Molecules

Chemistry. 2025 Jan 26:e202500120. doi: 10.1002/chem.202500120. Online ahead of print.

Authors

Yun Huang¹, Ruilong Zhang², Chengyu Shi³, Cong Wang⁴, Rui Liao², Chongwen Zou¹, Feng Wang², Ningdong Huang⁵

Affiliations

¹ USTC: University of Science and Technology of China, School of Nuclear Science and Technology, 230026, HEFEI, CHINA.
² USTC: University of Science and Technology of China, Key Laboratory of Precision and Intelligent Chemistry, Department of Polymer Science and Engineering, 230026, HEFEI, CHINA.
³ USTC: University of Science and Technology of China, National Synchrotron Radiation Laboratory,, 230026, HEFEI, CHINA.
⁴ USTC: University of Science and Technology of China, Key Laboratory of Precision and Intelligent Chemistry, Department of Polymer Science and Engineering, CHINA.
⁵ university of science and technology of china, School of Nuclear Science and Technology, China, 230029, HEFEI, CHINA.

PMID: 39865527
DOI: 10.1002/chem.202500120

Abstract

The final outcomes of supramolecular assembly are determined by the pathways and the formation of intermediates during the assembly process. We studied pathway complexity involving two consecutive pathways in supramolecular polymerization of naphthalene-diimide (NDI) derivative molecule. Depending on preparation methods anisotropic aggregates of J-type nanorods (Agg I) or more flexible H-type nanofibers (Agg II) are obtained from the identical initial state in solution of methyl cyclohexane (MCH) or MCH/CHCl3 mixtures. More interestingly intermediate aggregates driven by intra-molecular hydrogen-bonds are observed by spectroscopy and imaging techniques for both pathways. Thermodynamic model-fitting suggest that both pathways are consecutive ones with intermediate aggregates. Combining density functional theory (DFT) calculation results, we propose the molecular packing of Agg I and II. Our results reveal comprehensive pathway complexity in self-assembly of molecules as simple as NDI.

Keywords: Kinetic intermediates; Pathway complexity; Thermodynamic modeling; self-assembly in solution.