Controlling Asymmetry Amplification through Supramolecular Polymorphism.

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Tác giả: Lorenz Borsdorf, María Victoria Cappellari, Gustavo Fernandez, Alejandro Martínez-Manjarrés, Camila Montañez-Moyano, Cristian A Strassert, Yuncong Xue

Ngôn ngữ: eng

Ký hiệu phân loại: 341.442 +Rivers

Thông tin xuất bản: Germany : Angewandte Chemie (International ed. in English) , 2025

Mô tả vật lý:

Bộ sưu tập: NCBI

ID: 749298

Supramolecular polymorphism has recently emerged as a powerful concept, enabling a single chemical entity to form distinct, stable assemblies in solution with diverse morphological, photophysical, and electronic properties. Despite this progress, the interplay between supramolecular polymorphism and chirality remains unexplored. Herein, we harness supramolecular polymorphism to control the amplification of asymmetry in supramolecular polymerization (SP). For this purpose, we designed two Pt(II) complexes bearing π-extended ligands and S- or R-chiral side chains (compounds (S)-1 and (R)-1) that self-assemble into two distinct supramolecular polymorphs in methylcyclohexane: non-emissive short fibers with parallel molecular packing (AggI) and thermodynamically more stable helical fibers with a rotationally offset stacking, closer Pt···Pt contacts and weak 3MMLCT luminescence (AggII). These polymorphs exhibit markedly different amplification of asymmetry in majority rules (MR) and sergeants-and-soldiers (SaS) studies, with the thermodynamic polymorph displaying superior performance. Ultimately, co-assembly studies between the achiral model compound 2 -which exhibits strong 3MMLCT emission in the assembled state- and the chiral but weakly emissive AggII reveal a synergistic communication between chirality and luminescence, culminating in the emergence of circularly polarized luminescence (CPL). This study broadens the scope of supramolecular polymorphism and expands the design toolbox for adaptive supramolecular materials with emergent and synergistic functionalities.
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