正交分子幾何塑造電荷轉移拓撲：建立超分子功能的極簡結構途徑

Abstract

本研究旨在探討如何透過分子幾何設計與非共價作用力精準操控予體–受體（D–A）分子的自組裝、晶體堆疊及光物理與光催化功能。以 Pyrene–NDI 為模型系統，我們設計三種代表性構型：正交（o-NPC）、線性（l-NPC）及摺疊（f-NPC），並分析其在固態及共晶體系中的堆疊模式。結構分析顯示，幾何限制與 π–π 堆疊、CH–π 以及電荷轉移（charge-transfer）作用力的協同作用，可引導分子形成單通道或雙通道結構，其中雙通道排列可能有利於予體與受體之間的電子與電洞分離。光物理測試（吸收、穩態與時間解析光致放光）顯示，電荷轉移發光能量與壽命隨分子堆疊方式而異，反映出不同超分子結構下的電荷傳輸行為差異。進一步的光催化實驗表明，雙通道結構的 D–A 分子在可見光驅動下展現增強的反應活性。本研究提出一種結合分子幾何設計與非共價作用力的策略，用以調控 D–A 超分子自組裝行為，並進一步影響其光物理性質與光催化表現，為有機光電與光催化材料之設計提供新的設計思路。

This study aims to elucidate how molecular geometry design and non-covalent interactions can be employed to precisely control the self-assembly, crystal stacking, and photophysical and photocatalytic functions of donor–acceptor (D–A) molecules. Using the Pyrene–NDI system as a model, three representative conformations—orthogonal (o-NPC), linear (l-NPC), and folded (f-NPC)—were designed, and their stacking behaviors in the solid state and co-crystal systems were systematically investigated. Structural analyses reveal that the synergistic effects of geometric constraints, π–π stacking, CH–π interactions, and charge-transfer (CT) interactions direct the formation of single-channel or double-cable architectures, in which the double-cable arrangement may facilitate the separation of electrons and holes between donor and acceptor units. Photophysical studies, including absorption, steady-state, and time-resolved photoluminescence measurements, demonstrate that the CT emission energies and lifetimes are strongly dependent on the molecular stacking modes, while structural features further suggest a favorable influence on electron transport efficiency. Moreover, photocatalytic experiments show that D–A molecules adopting double-cable architectures exhibit enhanced visible-light-driven catalytic activity. This work provides a molecular design strategy that integrates geometry and non-covalent interactions to modulate supramolecular assembly, photophysical behavior, and photocatalytic performance of D–A systems, offering valuable insights for the development of organic optoelectronic and photocatalytic materials.