近日，香港中文大学 教授Qian Miao及其团队通过二氢重氮戊二烯N-乙炔基化修饰，实现了并戊二烯基有机半导体的分子轨道调谐。2025年1月21日出版的《美国化学会杂志》发表了这项成果。

该研究用6,13-二氢-6,13-重氮戊二烯的N,N'-二乙炔基化衍生物（2a和2b），探讨了有机半导体分子轨道调谐的概念。X射线晶体学证实，这些新分子与它们的母体并戊二烯衍生物（1a和1b），保持相同的分子几何形状和π-π堆叠。然而，它们在相位、节点性质和能级方面表现出改变的前沿分子轨道。

基于晶体结构的理论计算表明，2a和2b可以通过提高空穴转移积分显著提高母体化合物的空穴迁移率。研究人员用浸涂和棒状涂法制备了1a和2a的有机场效应晶体管（OFETs）。用于2a的两种类型的器件都显示出超过1 cm²·V^-1·s^-1的空穴迁移率，是用于1a的各自器件的两倍多。

此外，与它的母体并戊二烯不同的是，2a对可见光是透明的，并且对光和空气具有显着增强的环境稳定性，使其成为有机电子器件中更广泛应用的有希望的候选者。

附：英文原文

Title: Molecular Orbital Tuning of Pentacene-Based Organic Semiconductors through N-Ethynylation of Dihydrodiazapentacene

Author: Li Zhang, Yujie Zhao, Jiasheng Li, Yuang Fu, Boyu Peng, Jun Yang, Xinhui Lu, Qian Miao

Issue&Volume: January 21, 2025

Abstract: This study explores the concept of molecular orbital tuning for organic semiconductors through the use of N,N′-diethynylated derivatives of 6,13-dihydro-6,13-diazapentacene (2a and 2b). These novel molecules maintain the same molecular geometry and π–π stacking as their parent pentacene derivatives (1a and 1b), as confirmed by X-ray crystallography. However, they exhibit altered frontier molecular orbitals in terms of the phase, nodal properties, and energy levels. Theoretical calculations based on crystal structures indicate that 2a and 2b could significantly enhance the hole mobilities of the parent compounds by improving the hole transfer integral. Organic field-effect transistors (OFETs) of 1a and 2a were fabricated by using dip-coating and bar-coating methods. Both types of devices for 2a demonstrated a hole mobility exceeding 1 cm2 V–1 s–1, more than twice that of the respective devices for 1a. Additionally, unlike its pentacene parent, 2a is transparent to visible light and exhibits significantly enhanced environmental stability against light and air, making it a promising candidate for broader applications in organic electronic devices.

DOI: 10.1021/jacs.4c14775

Source:https://pubs.acs.org/doi/full/10.1021/jacs.4c14775