Tsukasa Irie

Topological simplification unlocks the first 4,3,3-connected tfe topology covalent organic framework, transforming high-connectivity reticular design into an unprecedented architecture for programmable wastewater purification.

The rational design of conversion‐kinetics‐promoting framework architectures offers a powerful strategy to overcome the polysulfide shuttling and sluggish conversion kinetics that limit lithium–sulfur (Li–S) batteries. Here, we report a new covalent organic framework, TUS‐44, constructed from tetrathiafulvalene‐based 4,4',4'',4'''‐([2,2'‐bi(1,3‐dithiolylidene)]‐4,4',5,5'‐tetrayl)tetraaniline and benzo[18]crown‐6‐derived 4,4′,4′′,4′′′‐(6,7,9,10,17,18,20,21‐octahydrodibenzo[ b , k ][1,4,7,10,13,16]hexaoxacyclooctadecine‐2,3,13,14‐tetrayl) tetrabenzaldehyde linkers. The resulting imine‐linked, π‐conjugated framework integrates heteroatom‐rich coordination sites within an electron‐delocalized π‐conjugated backbone, establishing a hierarchical, site‐specific interaction network (N > O > S) that governs Li ⁺ coordination, polysulfide anchoring, and dynamic charge redistribution. When coupled with conductive graphene to form an interfacial TUS‐44@G architecture, the hybrid layer functions as a chemisorptive, conversion‐kinetics‐promoting interface that regulates soluble polysulfides, facilitates interfacial charge‐transfer, and stabilizes intermediate species throughout cycling. This synergistic chemical–electronic coupling yields remarkable electrochemical performance: a high reversible capacity of 1455.7 mA h g ⁻¹ at 0.2 A g ⁻¹ , excellent rate capability of 773 mA h g ⁻¹ at 10 A g ⁻¹ , and outstanding durability with 0.034% capacity fading per cycle over 1000 cycles at 5 A g ⁻¹ . A Li–S pouch cell incorporating TUS‐44@G further delivers an outstanding initial energy density of ∼674 Wh kg ⁻¹ at 0.05 A g ⁻¹ (sulfur loading 44.558 mg), underscoring the practical potential of architecting conversion‐catalytic framework interfaces for high‐energy, durable Li–S batteries.

A ladder-structured silver cluster framework stabilized by tetrazine linkers enables selective and recyclable luminescence recognition of basic amino acids in water. The background image was generated using BRIA AI.

Dimension-engineered Cu ₁₀ cluster frameworks offer robust, recyclable luminescent responses for sensitive creatinine sensing in water.

TU-82, a 3D [8 + 2]-connected bcu COF, was post-synthetically metalated to yield TU-82-M ( M = Fe, Cu). TU-82-Fe shows outstanding activity and selectivity for electrocatalytic nitrate (NO ₃ ⁻ ) reduction to ammonia via atomically dispersed Fe sites.

This review highlights recent advances in covalent organic frameworks (COFs) as precision nanocarriers for targeted drug delivery, outlining their unique advantages, current challenges, and future opportunities in therapeutic applications.

Unlike 2D frameworks where conductivity is largely confined to in‐plane transport, the scu topology offers 3D conduction pathways that enhance bulk charge mobility. When integrated with redox‐active species like tetrathiafulvalene (TTF), the scu architecture promotes electron transfer across the 3D network, enabling tunable conductivity. This article presents the construction of a 3‐periodic (4,8)‐c covalent organic framework (COF), TU‐48, adopting a twofold interpenetrated scu net, achieved through the integration of a tetratopic D _2h ‐symmetric rectangular TTF structural motif and an octatopic D _2h ‐symmetric quadrangular prism linker. TU‐48 exhibits high structural order, well‐defined porosity, and redox‐responsive electrochemical behavior. The high‐connectivity 3D COF configuration ensures effective access to TTF redox centers, enabling controlled iodine oxidation and resulting in electrical conductivities of 4.3 × 10 ⁻⁶ S cm ⁻¹ at 298 K and 1.8 × 10 ⁻⁴ S cm ⁻¹ at 393 K. By demonstrating how enhanced structural connectivity in TTF‐bridged 3D covalent lattices enables improved charge‐transport properties, this research fuels innovation in sustainable energy storage solutions and electronics.

A chemically robust Ag ₁₂ -cluster material (TUS 8) exhibits exceptional aqueous photoluminescence and functions as a recyclable sensor for selective antibiotic detection in water.

The accelerating rise in atmospheric CO ₂ levels, driven by anthropogenic emissions, underscores the urgent need for transformative carbon management strategies. Photocatalytic and electrocatalytic CO ₂ reduction reactions (CO ₂ RRs) offer a promising route to valorize CO ₂ into energy‐rich fuels and chemical feedstocks, yet the intrinsic thermodynamic and kinetic barriers necessitate catalysts that combine high activity, selectivity, and durability. Recent breakthroughs in materials chemistry have spotlighted two emerging material classes—atomically precise metal nanoclusters (NCs) and extended reticular frameworks such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs)—as frontiers for next‐generation CO ₂ RR catalysts. Both systems offer unparalleled opportunities to engineer active sites at the atomic and molecular levels, enabling precise modulation of local environments, electronic structures, and substrate interactions. This review brings these two materials paradigms under a common vision of precision‐controlled catalysis, highlighting how innovations in cluster size, framework topology, and chemical functionality dictate product selectivity and C─C coupling behavior. We discuss emerging mechanistic insights, synthetic strategies, and structure–function relationships and outline challenges in conductivity, stability, and scalability. Finally, we propose integrated design principles to guide the development of hybrid platforms for efficient and selective CO ₂ valorization.

The accelerating rise in atmospheric CO ₂ levels, driven by anthropogenic emissions, underscores the urgent need for transformative carbon management strategies. Photocatalytic and electrocatalytic CO ₂ reduction reactions (CO ₂ RRs) offer a promising route to valorize CO ₂ into energy‐rich fuels and chemical feedstocks, yet the intrinsic thermodynamic and kinetic barriers necessitate catalysts that combine high activity, selectivity, and durability. Recent breakthroughs in materials chemistry have spotlighted two emerging material classes—atomically precise metal nanoclusters (NCs) and extended reticular frameworks such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs)—as frontiers for next‐generation CO ₂ RR catalysts. Both systems offer unparalleled opportunities to engineer active sites at the atomic and molecular levels, enabling precise modulation of local environments, electronic structures, and substrate interactions. This review brings these two materials paradigms under a common vision of precision‐controlled catalysis, highlighting how innovations in cluster size, framework topology, and chemical functionality dictate product selectivity and C─C coupling behavior. We discuss emerging mechanistic insights, synthetic strategies, and structure–function relationships and outline challenges in conductivity, stability, and scalability. Finally, we propose integrated design principles to guide the development of hybrid platforms for efficient and selective CO ₂ valorization.