Efficient room-temperature phosphorescence of covalent organic frameworks through covalent halogen doping

被引：159

作者：

Hamzehpoor, Ehsan ^{[1
]}

Ruchlin, Cory ^{[1
]}

Tao, Yuze ^{[1
]}

Liu, Cheng-Hao ^{[1
]}

Titi, Hatem M. ^{[1
]}

Perepichka, Dmytro F. ^{[1
]}

机构：

[1] McGill Univ, Dept Chem, Montreal, PQ, Canada

来源：

NATURE CHEMISTRY | 2023年 / 15卷 / 01期

基金：

加拿大自然科学与工程研究理事会;

关键词：

COORDINATION POLYMERS; CRYSTALLINE; PHOTOPHYSICS;

D O I：

10.1038/s41557-022-01070-4

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Organic room-temperature phosphorescence, a spin-forbidden radiative process, has emerged as an interesting but rare phenomenon with multiple potential applications in optoelectronic devices, biosensing and anticounterfeiting. Covalent organic frameworks (C0F5) with accessible nanoscale porosity and precisely engineered topology can offer unique benefits in the design of phosphorescent materials, but these are presently unexplored. Here, we report an approach of covalent doping, whereby a COF is synthesized by copolymerization of halogenated and unsubstituted phenyldiboronic acids, allowing for random distribution of functionalized units at varying ratios, yielding highly phosphorescent COFs. Such controlled halogen doping enhances the intersystem crossing while minimizing triplet-triplet annihilation by diluting the phosphors. The rigidity of the COF suppresses vibrational relaxation and allows a high phosphorescence quantum yield (empty set(Phos) <= 29%) at room temperature. The permanent porosity of the COFs and the combination of the singlet and triplet emitting channels enable a highly efficient COF-based oxygen sensor, with an ultra-wide dynamic detection range (similar to 10(3)-10(-5) torr of partial oxygen pressure).

引用

页码：83 / +

页数：9

共 58 条

[31]

Lee J, 2016, NAT MATER, V15, P92, DOI [10.1038/NMAT4446, 10.1038/nmat4446]

[32] Ultra-sensitive optical oxygen sensors for characterization of nearly anoxic systems [J].