Asymmetric Diphosphane Dioxides With A–π–A–π’–D Scaffolds for High‐Purity Deep‐Blue Luminescence
Abstract
Phosphane oxides represent a cornerstone unit in modern optoelectronic materials due to their strong electron-withdrawing character, high thermal stability, and ability to tune excited-state properties. Herein, we report a streamlined design strategy toward donor-π-acceptor-π'-acceptor (Γ-type) systems incorporating dual phosphane oxide units as both intermediate and terminal acceptors. A series of diphosphane dioxides (1-3) was synthesized and characterized, revealing pronounced deep-blue fluorescence (λem = 385-418 nm in toluene, λem = 415-457 nm in solid) that stems from charge-transfer and locally excited states with high photoluminescence yields up to 95%. Structure-property relationships demonstrate that subtle variations in π-conjugation (π = phenyl, biphenyl) and donor strength govern optical bandgap, oscillator strength, excited-state dipole moments, and intersystem crossing pathways. Notably, 2 and 3 exhibit favorable thermal stability and high triplet energies, enabling their application as emitters in deep-blue OLEDs. Devices based on 2 exhibit a maximum external quantum efficiency (EQE) of 4.86%, delivering high blue color purity with CIE coordinates of (0.15, 0.07), while maintaining low turn-on voltages and minimal efficiency roll-off. Transient electroluminescence studies indicate a significant contribution from triplet-triplet annihilation, enhancing exciton utilization beyond the conventional singlet limit.
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BibTeX
@article{hakkarainen2026asymmetric,
title = {{Asymmetric Diphosphane Dioxides With A–π–A–π’–D Scaffolds for High‐Purity Deep‐Blue Luminescence}},
author = {Eetu Hakkarainen and Zongying Liu and Jhon Sebastian Oviedo Ortiz and Nicolas Vanthuyne and Jeanne Crassous and Ondřej Mrózek and Fabien Cougnon and Wen‐yi Hung and Pi‐tai Chou and Igor O. Koshevoy and Andrey Belyaev},
journal = {Chemistry - A European Journal},
year = {2026},
month = oct,
doi = {10.1002/chem.71232},
url = {https://hal.science/hal-05676075v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Asymmetric Diphosphane Dioxides With A–π–A–π’–D Scaffolds for High‐Purity Deep‐Blue Luminescence
AU - Eetu Hakkarainen
AU - Zongying Liu
AU - Jhon Sebastian Oviedo Ortiz
AU - Nicolas Vanthuyne
AU - Jeanne Crassous
AU - Ondřej Mrózek
AU - Fabien Cougnon
AU - Wen‐yi Hung
AU - Pi‐tai Chou
AU - Igor O. Koshevoy
AU - Andrey Belyaev
PY - 2026
DA - 2026/10/14
JO - Chemistry - A European Journal
DO - 10.1002/chem.71232
UR - https://hal.science/hal-05676075v1
AB - Phosphane oxides represent a cornerstone unit in modern optoelectronic materials due to their strong electron-withdrawing character, high thermal stability, and ability to tune excited-state properties. Herein, we report a streamlined design strategy toward donor-π-acceptor-π'-acceptor (Γ-type) systems incorporating dual phosphane oxide units as both intermediate and terminal acceptors. A series of diphosphane dioxides (1-3) was synthesized and characterized, revealing pronounced deep-blue fluorescence (λem = 385-418 nm in toluene, λem = 415-457 nm in solid) that stems from charge-transfer and locally excited states with high photoluminescence yields up to 95%. Structure-property relationships demonstrate that subtle variations in π-conjugation (π = phenyl, biphenyl) and donor strength govern optical bandgap, oscillator strength, excited-state dipole moments, and intersystem crossing pathways. Notably, 2 and 3 exhibit favorable thermal stability and high triplet energies, enabling their application as emitters in deep-blue OLEDs. Devices based on 2 exhibit a maximum external quantum efficiency (EQE) of 4.86%, delivering high blue color purity with CIE coordinates of (0.15, 0.07), while maintaining low turn-on voltages and minimal efficiency roll-off. Transient electroluminescence studies indicate a significant contribution from triplet-triplet annihilation, enhancing exciton utilization beyond the conventional singlet limit.
SN - 0947-6539
SN - 1521-3765
ER -