Theoretical study of charge-transport and optical properties of organic crystals: 4,5,9,10-pyrenedi­imides

IUCrJ

Yu, K.¹  Huang, J.-D.²  Huang, X.³ 

[1] College of Medical Laboratory Science, Dalian Medical University, Dalian 116044, People's Republic of China;Key Laboratory of New Energy and Rare Earth Resource Utilization of State Ethnic Affairs Commission, School of Physics and Materials Engineering, Dalian Nationalities University, Dalian 116600, People's Republic of China;School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China

关键词: PYRENEDIIMIDES;    CHARGE-CARRIER MOBILITY;    TIME-DEPENDENT DENSITY FUNCTIONAL THEORY;    STRUCTURE-PROPERTY RELATIONSHIPS;   

DOI  :  10.1107/S2052252519004706

学科分类：数学（综合）

来源: International Union of Crystallography

【 摘 要 】

This work presents a systematic study of the conducting and optical properties of a family of aromatic di­imides reported recently and discusses the influences of side-chain substitution on the reorganization energies, crystal packing, electronic couplings and charge injection barrier of 4,5,9,10-pyrenedi­imide (PyDI). Quantum-chemical calculations combined with the Marcus–Hush electron transfer theory revealed that the introduction of a side chain into 4,5,9,10-pyrenedi­imide increases intermolecular steric interactions and hinders close intermolecular π–π stacking, which results in weak electronic couplings and finally causes lower intrinsic hole and electron mobility in t-C5-PyDI (μh = 0.004 cm2 V−1 s−1 and μe = 0.00003 cm2 V−1 s−1) than in the C5-PyDI crystal (μh = 0.16 cm2 V−1 s−1 and μe = 0.08 cm2 V−1 s−1). Furthermore, electronic spectra of C5-PyDI were simulated and time-dependent density functional theory calculation results showed that the predicted fluorescence maximum of t-C5-PyDI, corresponding to an S1→S0 transition process, is located at 485 nm, which is close to the experimental value (480 nm).

【 授权许可】

CC BY