The Meta-Link Rule Revisited: Relaxed Triplets and Non-Radiative Loss Decide Deep-Blue Phosphine-Oxide Hosts
Year: 2026
Type: preprint
Abstract: Deep-blue host design relies on a textbook rule: join the donor and the phosphine-oxide acceptor through a meta-phenylene link to break conjugation and keep the triplet energy high. Tested against experiment, the rule alone does not explain the measured photoluminescence-yield ordering. In a prespecified test on 36 deep-blue emitters, none of the tested radiative descriptors passes all four film-yield ranking criteria, and the meta-linked S1 host and the para-linked S4 host have overlapping apparent radiative-rate brackets yet differ 18-fold in apparent non-radiative rate. One calibrated excited-state protocol, applied to the hosts, their all-meta isomers and emitter pairs, shows that a meta break raises the vertical triplet energy and narrows the singlet–triplet gap, but the gain is lost on relaxation, and the vibronic displacement of the S1 state follows the measured yields. Screens for deep-blue hosts should therefore rank link positions by relaxed triplet energies, estimate non-radiative loss, and read a 1-eV computed gap as a property of locally excited states rather than as evidence against delayed fluorescence.
Source: ChemRxiv
Authors: Manmohan Dash, M. N. Satyanarayan
Institution: National Institute of Technology Karnataka
Language: English
Subfield: Electrical and Electronic Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7225095364