Confinement of Pyridine Derivatives into a Metal-Organic Framework Host as Electron Acceptors to Achieve Photoinduced Electron-Transfer.

The photoinduced electron-transfer (ET) process plays an irreplaceable role in chemical and biological fields exemplified by enzymatic catalysis, artificial photosystems, solar energy conversion, and so forth. Searching for a new photoinduced ET system is of great importance for the development of functional materials. Herein, a series of host-guest compounds based on a magnesium metal-organic framework (Mg-MOF) as a host and pyridine derivatives as guests have been presented. Notably, strong O-H···N hydrogen bond between the oxygen atom of µ2-H2O and the nitrogen atom of pyridine enables proton delocalization between water molecule and pyridine guest. Despite the absence of photochromic modules in these host-guest compounds, long-lived charge-separated states with distinct color changes can be formed after UV-light irradiation. The substituents in pyridines and the proton delocalization ability between the host and guests have a great influence on their photoinduced ET process to endow the MOF materials with tunable photoinduced charge-separated states.

One-pot Tandem Synthesis and Spontaneous Product Separation of N-heterocycles based on Bifunctional Small-molecule Photocatalyst.

Homogeneous and heterogeneous reactions wherein the resulting products remain dissolved in solvents generally require complicated separation and purification process, despite the advantage of heterogeneous systems allowing retrieval of catalysts. Herein, we have developed an efficient approach for the one-pot tandem synthesis of quinazolines, quinazolinones and benzothiadiazine 1,1-dioxides from alcohols and amines utilizing a bifunctional bipyridinium photocatalyst with redox and Lewis acid sites using air as an oxidant. Through solvent-modulation strategy, the photocatalytic system exhibits high performance and enables most products to separate spontaneously. Consequently, the homogeneous catalyst can be reused by direct centrifugation isolation of the products. Notably, the method is also applicable to the less active substrates, such as heterocyclic alcohols and aliphatic alcohols, and thus provides an efficient and environmentally friendly photocatalytic route with spontaneous separation of N-heterocycles to reduce production costs and meet the needs of atomic economy and green chemistry.

Photocatalyzed Oxidative Tandem Reaction Mediated by Bipyridinium for Multifunctional Derivatization of Alcohols.

The multifunctional derivatization of alcohols has been achieved by the bipyridinium-based conjugated small molecule photocatalysts with redox center and Lewis acid site. Besides exhibiting high activity in the selective generation of aldehydes/ketones, acids from alcohols through solvent modulation, this system renders the first selective synthesis of esters via an attractive cross-coupling pattern, whose reaction route is significantly different from the traditional condensation of alcohols and acids or esterification from hemiacetals. Following the oxidization of alcohol to aldehyde via bipyridinium-mediated electron and energy transfer, the Lewis acid site of bipyridinium then activates the aldehyde and methanol to obtain the acetal, which further reacts with methanol to generate ester. This method not only demonstrates a clear advantage of bipyridinium in diverse catalytic activities, but also paves the way for designing efficient multifunctional small molecule photocatalysts. This metal- and additive-free photocatalytic esterification reaction marks a significant advancement towards a more environmentally friendly, cost-effective and green sustainable approach, attributed to the utilization of renewable substrate alcohol and the abundant, low-cost air as the oxidant. The mildness of this esterification reaction condition provides a more suitable alternative for large-scale industrial production of esters.

Improved Effect of Metal Coordination on Molecular Oxygen Activation for Selective Aerobic Photooxidation.

A pyridinium-based complex with environment-friendly and earth-abundant ZnII ion was synthesized and explored as a green catalyst applied in activating molecular oxygen for the simple and efficient photooxidation of alcohols into aldehydes under additive-free and mild conditions. The metal coordination was conducive to promoting the electron transfer efficiency and introducing the heavy-atom effect for the increased generation of ⋅O2 - and 1 O2 . Accordingly, improved photocatalytic performance of this complex compared to its precursor, no matter activity or selectivity, was obtained, facilitating the transformation of alcohols into aldehydes in a sustainable way.

Photomechanical behavior triggered by [2 + 2] cycloaddition and photochromism of a pyridinium-functionalized coordination complex.

Photoinduced bending behavior triggered by [2 + 2] cycloaddition of a photoactive complex has been successfully achieved, accompanied by photochromic and fluorescence changes that provide convenience for long-distance observation of photomechanical motion. The key design feature is based on the introduction of flexible methylene groups and cation-π interactions. Moreover, the potential application in photomechanical devices was reflected by bending and supporting force experiments on the complex composite film, which is of increasing importance especially in soft actuators and robots.

Photoinduced-electron-transfer-driven surface modification to regulate adsorption behavior in a pyridinium-decorated metal-organic framework.

Surface modification based on a photo-induced electron transfer (PET) reaction in a pyridinium-decorated MOF material was found to be effective in regulating adsorption capacity. The current system enables the adsorption behavior to be manipulated based on variable affinity toward guest molecules through the redistribution of charge population with the preservation of the original pore structure, which is different from the prevalent approaches depending on photoinduced changes in molecular configurations of the pore backbone.