Steric hindrance modulated efficient thermally activated delayed fluorescence with non-linear optical, ferroelectric and piezoelectric properties

Abstract

Multi-carbazole-based benzonitrile systems are efficient thermally activated delayed fluorescence (TADF) materials for organic light-emitting diodes (OLEDs). However, they suffer from low PLQY due to the large dihedral angle arising from steric crowding. Addressing this challenge, we demonstrate a potent strategy to engineer steric crowding in this work. To achieve our goal, we have designed three luminogens, namely, CzPHCN, tCzPHCN and Cz2CzPHCN based on phenanthrene-9,10-dicarbonitrile (PHCN), as an acceptor core to minimize the steric hindrance between the donor groups. Among the three luminogens, tCzPHCN exhibits a maximum PLQY of 86% and the highest RISC rate of 3.5 × 105 s−1, the underlying cause being the least dihedral angle of 45.72° and suppressed intermolecular interaction due to the presence of the bulky tert-butyl group. Interestingly, our QM/MM calculations and experimental evidence suggest that the RISC process of both CzPHCN and tCzPHCN takes place via a hot exciton channel. Unlocking a new realm of applications, the unique non-centrosymmetric space group (Cmc21) of CzPHCN offers excellent SHG with a χ(2) value of 0.21 pm V−1 at 1320 nm. In addition to this, the molecule depicts good ferroelectric (PS = 0.32 μC cm−2), piezoelectric energy harvesting (VOC = 2.8 V) and two-photon absorption properties.

Graphical abstract: Steric hindrance modulated efficient thermally activated delayed fluorescence with non-linear optical, ferroelectric and piezoelectric properties

Supplementary files

Article information

Article type
Edge Article
Submitted
18 Mar 2025
Accepted
27 May 2025
First published
27 May 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2025, Advance Article

Steric hindrance modulated efficient thermally activated delayed fluorescence with non-linear optical, ferroelectric and piezoelectric properties

M. Dutta, A. Chatterjee, N. Deka, R. Tanwar, V. Mishra, A. Saha, P. Mandal, R. Boomishankar and P. Hazra, Chem. Sci., 2025, Advance Article , DOI: 10.1039/D5SC02107C

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