Direct Construction of Isomeric Benzobisoxazole-Vinylene-Linked Covalent Organic Frameworks with Distinct Photocatalytic Properties.
J Am Chem Soc
; 144(30): 13953-13960, 2022 Aug 03.
Article
em En
| MEDLINE
| ID: mdl-35877552
ABSTRACT
Vinylene/olefin-linked two-dimensional covalent organic frameworks (v-2D-COFs) have emerged as advanced semiconducting materials with excellent in-plane conjugation, high chemical stabilities, and precisely tunable electronic structures. Exploring new linkage chemistry for the reticular construction of v-2D-COFs remains in infancy and challenging. Herein, we present a solid-state benzobisoxazole-mediated aldol polycondensation reaction for the construction of two novel isomeric benzobisoxazole-bridged v-2D-COFs (v-2D-COF-NO1 and v-2D-COF-NO2) with trans and cis configurations of benzobisoxazole. Interestingly, the isomeric benzobisoxazole linkers endow the two v-2D-COFs with distinct optoelectronic and electrochemical properties, ranging from light absorption and emission to charge-transfer properties. When employed as the photocathode, v-2D-COF-NO1 exhibits a photocurrent of up to â¼18 µA/cm2 under AM 1.5G irradiation at -0.3 V vs reversible hydrogen electrode (RHE), which is twice the value of v-2D-COF-NO2 (â¼9.1 µA/cm2). With Pt as a cocatalyst, v-2D-COF-NO1 demonstrates a photocatalytic hydrogen evolution rate of â¼1.97 mmol h-1 g-1, also in clear contrast to that of v-2D-COF-NO2 (â¼0.86 mmol h-1 g-1) under identical conditions. This work demonstrates the synthesis of v-2D-COFs via benzobisoxazole-mediated aldol polycondensation with isomeric structures and distinct photocatalytic properties.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2022
Tipo de documento:
Article
País de afiliação:
China