Zhu Danmei, Gai Xinwen, Zou Yi, Jin Ying, Wang Jingang
College of Science, Liaoning Petrochemical University, Fushun 113001, China.
Molecules. 2025 Jul 25;30(15):3127. doi: 10.3390/molecules30153127.
In this study, three alternating donor-acceptor (D-A) type [12]cycloparaphenylene ([12]CPP) derivatives ([12]CPP 1a, 2a, and 3a) were designed through precise molecular engineering, and their multidimensional photophysical responses and chiroptical properties were systematically investigated. The effects of the alternating D-A architecture on electronic structure, excited-state dynamics, and optical behavior were elucidated through density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The results show that the alternating D-A design significantly reduced the HOMO-LUMO energy gap (e.g., 3.11 eV for [12]CPP 2a), enhanced charge transfer characteristics, and induced pronounced red-shifted absorption. The introduction of an imide-based acceptor ([12]CPP 2a) further strengthened the electron push-pull interaction, exhibiting superior performance in two-photon absorption, while the symmetrically multifunctionalized structure ([12]CPP 3a) predominantly exhibited localized excitation with the highest absorption intensity but lacked charge transfer features. Chiral analysis reveals that the alternating D-A architecture modulated the distribution of chiral signals, with [12]CPP 1a displaying a strong Cotton effect in the low-wavelength region. These findings not only provide a theoretical basis for the molecular design of functionalized CPP derivatives, but also lay a solid theoretical foundation for expanding their application potential in optoelectronic devices and chiral functional materials.
在本研究中，通过精确的分子工程设计了三种交替供体-受体（D-A）型[12]环对亚苯基（[12]CPP）衍生物（[12]CPP 1a、2a和3a），并系统地研究了它们的多维光物理响应和手性光学性质。通过密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）计算阐明了交替D-A结构对电子结构、激发态动力学和光学行为的影响。结果表明，交替D-A设计显著降低了HOMO-LUMO能隙（例如，[12]CPP 2a为3.11 eV），增强了电荷转移特性，并导致明显的红移吸收。基于酰亚胺的受体（[12]CPP 2a）的引入进一步加强了电子推拉相互作用，在双光子吸收方面表现出优异性能，而对称多官能化结构（[12]CPP 3a）主要表现出具有最高吸收强度的局域激发，但缺乏电荷转移特征。手性分析表明，交替D-A结构调节了手性信号的分布，[12]CPP 1a在低波长区域显示出强烈的科顿效应。这些发现不仅为功能化CPP衍生物的分子设计提供了理论基础，也为扩大其在光电器件和手性功能材料中的应用潜力奠定了坚实的理论基础。
