Photocatalytic Hydrogen Peroxide Production through Functionalized Semiconductive Metal-Organic Frameworks.

Hydrogen peroxide (H2O2) holds significance as a vital chemical with the potential to serve as an energy carrier. Compared with the conventional anthraquinone process, photocatalytic H2O2 production has emerged as an appealing alternative because of its energy efficiency and environmental sustainability. However, the existing photocatalysts suffer from low catalytic efficiency, limited tunability of optical properties, and reliance on sacrificial agents due to high energy loss caused by inefficient charge separation. Therefore, developing catalysts with tunable optical properties and efficient charge separation is desirable. In this work, we introduce postsynthetic functionalization into an electrically conductive metal-organic framework, namely, DPT-MOF. Leveraging DPT (3,6-di(4-pyridyl)-1,2,4,5-tetrazine) as a pillar ligand, we exploited click-type chemistry to manipulate band position and charge separation efficiency, allowing for photocatalytic nonsacrificial H2O2 production. Notably, the fluorine-functionalized MOF exhibited the highest H2O2 production rate of 1676 µmol g-1 h-1 under visible light in O2-saturated water among our other samples. This high production rate is attributed to the tuned electronic structure and prolonged charge lifetime facilitated by the fluorine groups. This work highlights the effectiveness of postsynthetic methodology in tuning optical properties, opening a promising avenue for advancing the field of semiconductive MOF-based photocatalysis.

Maximizing the Potential of Electrically Conductive MOFs.

ConspectusElectrically conductive metal-organic frameworks (EC-MOFs) have emerged as a compelling class of materials, drawing increasing attention due to their unique properties facilitating charge transport within porous structures. The synergy between electrical conductivity and porosity has opened a wide range of applications, including electrocatalysis, energy storage, chemiresistive sensing, and electronic devices that have been underexplored for their insulating counterparts. Despite these promising prospects, a prevalent challenge arises from the predominant adoption of two-dimensional (2D) structures by most EC-MOFs. These 2D frameworks often show modest surface areas and short interlayer distances, hindering molecular accessibility, which deviates from the inherent characteristics of conventional MOFs. Furthermore, the quest for efficient charge transport imposes design constraints, leading to a restricted selection of functional building blocks. Additionally, there is a lack of established functionalization methods within EC-MOFs, limiting their functional diversity. Thus, these challenges have impeded EC-MOFs from reaching their full potential.In this Account, we summarize and discuss our group's efforts aimed at enhancing molecular accessibility and deploying the functional diversity of EC-MOFs. Our focus on enhancing molecular accessibility involves several strategies. First, we employed macrocyclic ligands with intrinsic pockets as the building blocks for EC-MOFs. The integrated intrinsic pockets in the frameworks supplement surface areas and additional pores to enhance molecular accessibility. The resulting macrocyclic ligand-based EC-MOFs exhibit exceptionally high surface areas and confer advantages in electrochemical performances. Second, our efforts extend to addressing the structural limitations, frequently associated with EC-MOFs' 2D structures. Through the pillar insertion strategy, we transformed a 2D EC-MOF platform into a three-dimensional (3D) structure, thereby achieving higher porosity and enhanced molecular accessibility. In pursuing functional diversity, we have delved into molecular-level tuning of EC-MOF building blocks. We demonstrated that electron-rich alkyne-based pockets in the macrocyclic ligands can host transition metals and alkali ions, enabling ion selectivity and showcasing diverse use of EC-MOFs. We utilized a postsynthetic approach to further functionalize metal nodes on the molecular level within an EC-MOF framework, introducing a proton-conducting pathway while preserving its electrical conductivity.We aspire for this Account to provide practical insights and strategies to surmount structural and functional diversity limitations in the realm of EC-MOFs. By integrating enhanced molecular accessibility and diverse functionality, our endeavor to propel the utility of these materials will inspire further rational development for future EC-MOFs and unlock their full potential.

Imparting Functionality and Enhanced Surface Area to a 2D Electrically Conductive MOF via Macrocyclic Linker.

The development of 2D electrically conductive metal-organic frameworks (EC-MOFs) has significantly expanded the scope of MOFs' applications into energy storage, electrocatalysis, and sensors. Despite growing interest in EC-MOFs, they often show low surface area and lack functionality due to the limited ligand motifs available. Herein we present a new EC-MOF using 2,3,8,9,14,15-hexahydroxyltribenzocyclyne (HHTC) linker and Cu nodes, featuring a large surface area. The MOF exhibits an electrical conductivity up to 3.02 × 10-3 S/cm and a surface area up to 1196 m2/g, unprecedentedly high for 2D EC-MOFs. We also demonstrate the utilization of alkyne functionality in the framework by postsynthetically hosting heterometal ions (e.g., Ni2+, Co2+). Additionally, we investigated particle size tunability, facilitating the study of size-property relationships. We believe that these results not only contribute to expanding the library of EC-MOFs but shed light on the new opportunities to explore electronic applications.

From 2D to 3D: Postsynthetic Pillar Insertion in Electrically Conductive MOF.

The emergence of 2D electrically conductive metal-organic frameworks (MOFs) has significantly expanded the scope of metal-organic framework applications from electrochemical energy storage to electronic devices. However, their potentials are not fully exploited due to limited accessibility to internal pores in stacked 2D structures. Herein we transform a 2D conjugated MOF into a 3D framework via postsynthetic pillar-ligand insertion. Cu-THQ was chosen due to its ability to adopt additional ligands at the axial positions at the copper nodes. Cu-THQ demonstrates that structural augmentation increases ion accessibility into internal pores, resulting in an increased gravimetric capacitance up to double that of the pristine counterpart. Beyond this, we believe that our findings can further be used to functionalize the existing 2D conductive MOFs to offer more opportunities in sensing, electronic, and energy-related applications by utilizing additional functions and increased accessibility from the pillars.

Trisulfur-Radical-Anion-Triggered C(sp2)-H Amination of Electron-Deficient Alkenes.

A trisulfur-radical-anion (S3̇-)-triggered C(sp2)-H amination of α,ß-unsaturated carbonyl derivatives with simple amines has been demonstrated. This protocol provides convenient access to a variety of synthetically valuable N-unprotected and secondary ß-enaminones with absolute Z selectivity and tertiary ß-enaminones with E selectivity. Mechanistic probe and electronic structure theory calculations suggest that S3̇- initiates the nucleophilic attacks via a thiirane intermediate.

Functionalization of C-H bonds in acetophenone oximes with arylacetic acids and elemental sulfur.

Fused thieno[3,2-d]thiazoles were synthesized via a coupling of acetophenone ketoximes, arylacetic acids, and elemental sulfur in the presence of Li2CO3 base. Functionalities including chloro, bromo, fluoro, trifluoromethyl, and pyridyl groups were compatible with reaction conditions. High yields and excellent regioselectivities were obtained even if meta-substituted ketoxime acetates were used. Ethyl esters of heteroarylacetic acids were competent substrates, which is very rare in the literature. Our method would offer a convenient protocol to afford polyheterocyclic structures from simple substrates.

Homo- and Heteroannulation of sp3 C-H Bonds in Acetophenones for Divergent Synthesis of Thienothiazoles.

A synthesis of fused thieno[3,2-d]thiazoles via direct functionalization of C(sp3)-H bonds in acetophenones was reported. The transformation is divergent to afford either 2-phenylbenzo[4,5]thieno[3,2-d]thiazoles or benzo[4,5]thieno[3,2-d]thiazol-2-yl(phenyl)methanones. Cross-coupling of acetophenones with C-H bonds in phenylacetic acids, methylazaarenes, and aldehydes was also feasible. Excellent tolerance of functionalities was observed. Our method marks a rare functionalization of C(sp3)-H bonds in acetophenones to obtain heterocycles in the absence of prefunctionalized oxime esters.