A Photosensitizing Metal–Organic Framework as a Tandem Reaction Catalyst for Primary Alcohols from Terminal Alkenes and Alkynes

Abstract

Owing to the wide and growing demand for primary alcohols, the development of efficient catalysts with high regioselectivity remains a worthwhile pursuit. However, according to Markovnikov's rule, it is a challenge to obtain primary alcohols with high yields and regioselectivity from terminal alkenes or alkynes. Herein, we report the synthesis of a photosensitizing two‐dimensional (2D) metal–organic framework (MOF) from cyclic trinuclear copper(I) units (Cu‐CTUs) and a boron dipyrro‐methene (Bodipy) ligand. The MOF features broadband light absorption, excellent photoinduced charge separation efficiency, and photochemical properties. By integrating the copper‐catalyzed hydroboration and photocatalyzed aerobic oxidation, it can catalyze terminal alkenes and alkynes to produce primary alcohols via a one‐pot tandem reaction with excellent regioselectivity, good overall yields in two‐step reactions (up to 85 %), broad substrate compatibility (32 examples) and good reusability under mild conditions.

Imine-linked donor–acceptor metal–organic frameworks for an efficient photocatalytic oxidative coupling reaction

“…18,19 Recently, by combining the chemistry of MOFs and covalent organic frameworks (COFs), 20 we and other groups have successfully synthesized various functional CTU-based MOFs linked by dynamic covalent bonds, which allows us to bring the merits from MOFs and COFs. 21–29 Due to the built-in characteristics, CTU-based MOFs exhibit not only highly ordered structures and controllable porosities, but also unique catalytic activity for various organic transfer reactions. 26–29 It has been found that Cu( i ) CTUs exhibited an electron-deficient surface, 30 which can be used as electron acceptor building blocks to construct D–A MOFs via dynamic covalent chemistry.…”

Panchromatic Light-Harvesting Three-Dimensional Metal Covalent Organic Frameworks for Boosting Photocatalysis

“…Photosensitization is a crucial step for realizing light-to-chemical energy conversion in photosynthesis, and the development of efficient light-harvesting systems (LHSs) is highly desirable. − In principle, promising LHSs should feature combinational merits, including broadband light absorption for solar energy utilization, order architectures for electron and energy transfer, and multiple functional moieties for synergism. To meet these requirements, various crystalline LHSs have been exploited, such as metal–organic framework (MOFs), − covalent organic framework (COFs), − and supramolecular systems. − Unfortunately, in most of the LHSs, only the monochromophore was used as a photosensitizer (PS), showing limited solar spectral absorption for practical photocatalytic application.…”

Metal-ion-determined geometrical configurations of metallo-cages with different emission properties

“…17,18 Inspired by the functional complexity of biomolecular systems, different metal ions have been introduced into the metallo-cages with aim to prepare highly advanced structures as well as fulfil specific applications. 19–22…”