Mixed-valence metal–organic frameworks: concepts, opportunities, and prospects

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 20, 2024

Mixed-valence MOFs have exhibited unique features in different practical fields, resulting from long-range charge delocalization and a tunable band gap within the framework.

Language: Английский

---

Two-Dimensional Organic–Inorganic van der Waals Hybrids

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

Two-dimensional organic-inorganic (2DOI) van der Waals hybrids (vdWhs) have emerged as a groundbreaking subclass of layer-stacked (opto-)electronic materials. The development 2DOI-vdWhs via systematically integrating inorganic 2D layers with organic crystals at the molecular/atomic scale extends capabilities traditional vdWhs, thanks to their high synthetic flexibility and structural tunability. Constructing an hybrid interface atomic precision will unlock new opportunities for generating unique interfacial transport properties by combining strengths layers, thus allowing us satisfy growing demand multifunctional applications. Here, this review provides comprehensive overview latest advancements in chemical synthesis, characterization, numerous applications 2DOI-vdWhs. Firstly, we introduce chemistry physical recently rising (O2DCs), which feature crystalline nanostructures comprising carbon-rich repeated units linked covalent/noncovalent bonds exhibit strong in-plane extended π-conjugation weak interlayer vdWs interaction. Simultaneously, representative (I2DCs) are briefly summarized. After that, strategies be summarized, including synthesizing single-component O2DCs dimensional control vdWhs I2DCs. With these approaches, dimension, stacking modes, composition highlighted. Subsequently, special focus given on discussion optical electronic materials closely relevant structures, so that can establish general structure-property relationship In addition properties, devices such transistors, photodetectors, sensors, spintronics, neuromorphic well energy discussed. Finally, provide outlook discuss key challenges future development. This aims foundational understanding inspire further innovation next-generation transformative technological potential.

Language: Английский

---

2D Undulated Metal Hydrogen-Bonded Organic Frameworks with Self-Adaption Interlayered Sites for Highly Efficient C–C Coupling in the Electrocatalytic CO2 Reduction

Nano-Micro Letters, Journal Year: 2025, Volume and Issue: 17(1)

Published: Feb. 24, 2025

Abstract The hydrogen-bonded organic frameworks (HOFs) as a new type of porous framework materials have been widely studied in various areas. However, the lack appropriate active sites, low intrinsic conductivity, and poor stability limited their performance field electrocatalysis. Herein, we designed two 2D metal (2D–M–HOF, M = Cu 2+ or Ni ) with coordination compounds based on 2,3,6,7,14,15-hexahydroxyl cyclotricatechylene transition ions (Cu ), respectively. crystal structure 2D–Cu–HOF is determined by continuous rotation electron diffraction, indicating an undulated hydrogen-bond network interlayered π-π stacking. flexible 2D–M–HOF leads to formation self-adaption resulting superior activity selectivity electrocatalytic conversion CO 2 C products, achieving total Faradaic efficiency exceeding 80% due high-efficiency C–C coupling. experimental results density functional calculations verify that enables energetically favorable *OCCHO intermediate. This work provides promising strategy for designing HOF catalysts electrocatalysis related processes.

Language: Английский

---

A Trimming‐π Strategy for Constructing Functional Conductive Metal–Organic Frameworks Using Metalloporphyrazine Units

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Abstract Developing functional metal–organic frameworks (MOFs) with high electrical conductivity is crucial for their applications as advanced electronic materials. In this work, we the first time construct a new family of and highly conductive MOFs using metalloporphyrazine (MPz) ligands based on trimming‐π concept via cutting benzene ring from molecular metallopthalocynine (MPc). The deprotonation‐after‐coordination synthetic method affords crystalline MPz−Cu−NH square lattices. Four‐point probe measurements reveal room temperature MPz‐based ranging 3.5×10 −2 to 1.3×10 −1 S cm , two orders magnitude higher than MPc‐based MOF counterparts. Temperature‐dependent band structure analysis demonstrate ultra‐small activation energies potential metallic conducting behavior MOFs. Encapsulation aromatic guest molecules different electron‐donating ‐withdrawing features allows modulation CuPz−Cu−NH in wide range spanning magnitude. These built‐in MPz units exhibit identity‐dependent sensing performance, realize sensitive detection NH 3 NO 2 low driving voltage 0.1 V.

Language: Английский

---

Ligand‐Insertion Strategy for Constructing 2D Conjugated Metal‐Organic Framework with Large Pore Size for Electrochemical Analytics

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 25, 2024

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have shown great promise in various electrochemical applications due to their intrinsic electrical conductivity. A large pore aperture is a favorable feature of this type material because it facilitates the mass transport chemical species and electrolytes. In work, we propose ligand insertion strategy which linear inserted into linkage between multitopic ligands, extending metal ion unit -M-ligand-M-, for construction 2D c-MOFs with apertures, utilizing only small ligands. As proof-of-concept trial strategy, c-MOF mesopores 3.2 nm was synthesized using commercially available ligands hexahydrotriphenylene 2,5-dihydroxybenzoquinone. The facilitation diffusion redox by size MOF demonstrated through series probes. With feature, showed superior performance analysis variety biological species.

Language: Английский

---

A Wearable Electrochemical Sensor Based on Single-Atom Pt Anchored on Activated NiCo-LDH/Ti₃C₂T_x for Real-Time Monitoring of Glucose

Analytical Chemistry, Journal Year: 2024, Volume and Issue: 96(45), P. 18239 - 18245

Published: Nov. 4, 2024

Wearable, noninvasive sweat sensors enable real-time monitoring of metabolites in human health management. However, the commercial enzyme-based and currently nonenzymatic glucose sensor represents sluggish oxidation kinetics a narrow sensing range. Rational design sensitive materials is significant yet faces huge challenge. Herein, we construct single-atom Pt supported on NiCo-LDH/Ti

Language: Английский

---

Catalytic N‐Formylation of CO2 by Atomically Precise Au8Pd1(DPPF)42+ Clusters into a Two‐Dimensional Metal‐Organic Framework

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 13, 2024

By highly efficient ligand-exchange strategy, atomically precise Au

Language: Английский

---

Catalytic N‐Formylation of CO2 by Atomically Precise Au8Pd1(DPPF)42+ Clusters into a Two‐Dimensional Metal‐Organic Framework

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 13, 2024

Abstract By highly efficient ligand‐exchange strategy, atomically precise Au 8 Pd 1 (PPh 3 ) 2+ =triphenylphosphine) cluster can be transformed into a (DPPF) 4 (DPPF=1,1′‐bis(diphenylphosphino)ferrocene) that maintain the atomic‐packing structure but overcome lability of . Catalytic evaluation for CO 2 hydrogenation coupled with o‐phenylenediamine demonstrates catalyst remarkably enhance both activity and stability compared to catalyst. More notably, direct construction two‐dimensional metal–organic framework (2D MOF) elaborately accomplished in formylation process o‐phenylenediamine, H zinc nitrate enabled by The 2D MOF further enables capture transformation combine organic synthesis epoxides under mild conditions. This work provides opportunities creating active sites chemical recycling

Language: Английский

---

Efficient one-step synthesis of diarylacetic acids by electrochemical direct carboxylation of diarylmethanol compounds in DMSO

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2392 - 2400

Published: Sept. 20, 2024

An efficient one-step synthesis of diarylacetic acids was successfully performed by electrochemical direct carboxylation diarylmethanol compounds in DMSO. Constant-current electrolysis species DMSO using a one-compartment cell equipped with Pt cathode and Mg anode the presence carbon dioxide induced reductive C(sp 3 )−O bond cleavage at benzylic position subsequent fixation to produce good yield. This protocol provides novel simple approach from without transformation hydroxy group into appropriate leaving groups, such as halides esters including carbonates.

Language: Английский

---

Ligand‐Insertion Strategy for Constructing 2D Conjugated Metal‐Organic Framework with Large Pore Size for Electrochemical Analytics

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 25, 2024

Abstract Two‐dimensional conjugated metal–organic frameworks (2D c ‐MOFs) have shown great promise in various electrochemical applications due to their intrinsic electrical conductivity. A large pore aperture is a favorable feature of this type material because it facilitates the mass transport chemical species and electrolytes. In work, we propose ligand insertion strategy which linear inserted into linkage between multitopic ligands, extending metal ion unit ‐M‐ligand‐M‐, for construction 2D ‐MOFs with apertures, utilizing only small ligands. As proof‐of‐concept trial strategy, ‐MOF mesopores 3.2 nm was synthesized using commercially available ligands hexahydrotriphenylene 2,5‐dihydroxybenzoquinone. The facilitation diffusion redox by size MOF demonstrated through series probes. With feature, showed superior performance analysis variety biological species.

Language: Английский

---