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Effect of Bulky Functional Groups on Donor and Acceptor Interactions and their Photoluminescence Properties
Author(s) -
Woon Kai Lin,
Mustapa Siti Aisyah Syaerah,
Mohd Jamel Nor Shafiq,
Lee Vannajan Sanghiran,
Zakaria Muhammad Zhafran,
Ariffin Azhar
Publication year - 2020
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.202000612
Subject(s) - photoluminescence , acceptor , density functional theory , chemistry , materials science , chemical physics , photochemistry , computational chemistry , nanotechnology , optoelectronics , condensed matter physics , physics
Material designs that use donor and acceptor units are often found in organic optoelectronic devices. Molecular level insight into the interactions between donors and acceptors are crucial for understanding how such interactions can modify the optical properties of the organic optoelectronic materials. In this paper, tris(4‐( tert ‐butyl)phenyl)amine ( p TPA) was synthesized as a donor in order to compare with unmodified triphenylamine (TPA) in a donor–acceptor system by having 2,4,6‐triphenyl‐1,3,5‐triazine (TRZ) as an acceptor. Dimerization of donors and acceptors occurred in solvent when the concentration of solute is high. At 0 K, using a polarizable continuum model, the nitrogen atom of TPA is found to stack on top of the center of triazine of TRZ, whereas such alignment is offset in p TPA and TRZ. We attributed such alignment in TPA‐TRZ as the result of attractive interactions between partial localization of 2p z electrons at the nitrogen atom of TPA and the π deficiency of triazine in TPA‐TRZ. By taking into account random motions of the solvent effect at 300 K in quantum molecular dynamics and classical molecular dynamics simulations to interpret the marked difference in emission spectra between TPA‐TRZ and p TPA‐TRZ, it was revealed that the attractive interaction between p TPA and TRZ in toluene is weaker than TPA and TRZ. Because of the weaker attractive interaction between p TPA and TRZ in toluene, the dimers adopted numerous ground state conformations resulting in broad emission bands superimposed with multiple small Gaussian peaks. This is in contrast to TPA‐TRZ which has only one dominant dimer conformation. This study demonstrates that the strength of intermolecular interactions between donors and acceptors should be taken into consideration in designing supramolecular structures.