Authorship：Lead author   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry (RSC)  

This study provides a new design principle for molecule-based heterogeneous catalysts, in which proton transport, CO ₂ accumulation, and molecular catalysis are integrated within a single crystalline framework.

DOI： 10.1039/d5sc10220k

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Publishing type：Research paper (scientific journal)   Publisher：Wiley  

Direct carboxylation of C(sp ³ )H bonds with carbon dioxide (CO ₂ ) offers an attractive route to value‐added carboxylic acids but remains challenging due to the inertness of both reaction partners. Here, we report a fundamentally distinct electrochemical strategy that enables carboxylation of dibenzylic C(sp ³ )H bonds using hydrogen atom transfer (HAT) species reductively generated at the cathode. This represents a rare example of C(sp ³ )H bond functionalization mediated by cathodically generated HAT species. In contrast to anodic HAT systems that require interelectrode diffusion of reactive intermediates, the present method allows all the elementary steps (HAT species generation, C(sp ³ )H bond cleavage, and CO ₂ incorporation) to occur at the same cathode. Consequently, the reaction proceeds efficiently under mild conditions (room temperature, 1 atm CO ₂ ) without requiring an external sacrificial redox reagent, affording carboxylation products in good yields (up to 69%) within a short reaction time (2 h). Mechanistic studies support a pathway involving sequential electron transfer‐chemical reaction (EC) and CO ₂ ‐coupled electron transfer processes for HAT species generation. This work establishes a mechanistically defined platform for electrochemical dibenzylic C(sp ³ )H bond functionalization.

DOI： 10.1002/celc.202600014

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Other Link： https://chemistry-europe.onlinelibrary.wiley.com/doi/full-xml/10.1002/celc.202600014

Publishing type：Research paper (scientific journal)   Publisher：Wiley  

ABSTRACT

The development of efficient molecular catalysts for photochemical CO ₂ reduction is a central challenge in artificial photosynthesis. The efficiency of this reaction depends on three critical elementary processes, namely light harvesting, electron transfer, and proton transfer. To realize efficient catalysts, the catalytic system for photochemical CO ₂ reduction should include following three functions: light‐harvesting, electron‐accumulating, and proton‐supply. However, creating a single molecular system that simultaneously integrates all three functions remains challenging. In this study, a novel iron porphyrin complex, 5,10,15,20‐tetrakis[4‐( N ‐(pentan‐3‐yl)‐1,4,5,8‐naphthalenetetracarboxylic diimide‐ N ‐yl)phenyl] porphyrinato iron(III) chloride ( FeNDI ), was developed which successfully incorporates these three key functions through the incorporation of naphthalene diimide (NDI) moieties at the porphyrin meso ‐positions. FeNDI exhibits intrinsic light‐harvesting ability, enabling the reaction to proceed without external photosensitizers. Additionally, it demonstrates electron‐accumulating ability, which enhances catalytic durability, while also exhibiting proton‐supply ability, which allows the interaction between the coordinated CO ₂ species and proton‐supplying sites. Consequently, this complex achieved a turnover number of 611 for CO production, which is the highest value reported to date among relevant systems. This study therefore demonstrates the successful integration of all the three essential functions into a single catalyst molecule, offering a powerful strategy for the design of high‐performance solar energy conversion systems.

DOI： 10.1002/cctc.70684

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Other Link： https://chemistry-europe.onlinelibrary.wiley.com/doi/full-xml/10.1002/cctc.70684

Publishing type：Research paper (scientific journal)   Publisher：Oxford University Press (OUP)  

Abstract

We report a supramolecular framework constructed from an iridium(III)-porphyrin complex through self-assembly driven by non-covalent interactions. The afforded crystalline material features an ordered porous structure and isolated emissive centers. This framework exhibits sharp near infrared phosphorescence in the solid state, and the emission bands were narrower than those of the relevant amorphous solid, demonstrating importance of isolated emissive centers.

DOI： 10.1093/chemle/upaf242

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Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

DOI： 10.1016/j.cocr.2025.100017

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Authorship：Lead author  

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Authorship：Lead author  

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Event date： 2022.12

Presentation type：Oral presentation (invited, special)  

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Presentation type：Oral presentation (invited, special)  

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