Electrically conductive [Fe<sub>4</sub>S<sub>4</sub>]-based organometallic polymers

Kadota, Kentaro; Chen, Tianyang; Gormley, Eoghan L.; Hendon, Christopher H.; Dincă, Mircea; Brozek, Carl K.

doi:10.1039/d3sc02195e

Cited by 3 publications

(2 citation statements)

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“…34−36 Combining [Fe 4 S 4 ] clusters and ditopic Nheterocyclic carbene linkers leads to amorphous conductive materials. 37 Our laboratory has also used [Fe 4 S 4 ] clusters to design well-defined crystalline coordination polymers (CPs) with [Fe 4 S 4 ] clusters and 1,4-benzenedithiolate (BDT). 38,39 Importantly, this 1D coordination polymer, [(Fe 4 S 4 )(BDT) 2 ]-[TMA] 2 (Fe CP , TMA = tetramethylammonium), is soluble in dimethylformamide (DMF) which suggests that solution processing should be possible, for instance with drop-casting onto an electrode.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Several [Fe 4 S 4 ] clusters have been embedded in polymeric supports such as polystyrene and cyclodextrins. , Graphene also supports [Fe 4 S 4 ] clusters and the resultant composite materials show electrocatalytic hydrogen evolution activity . Chalcogels composed of metal–sulfur clusters including [Fe 4 S 4 ] clusters also serve as catalysts for several reductive processes. − Combining [Fe 4 S 4 ] clusters and ditopic N-heterocyclic carbene linkers leads to amorphous conductive materials . Our laboratory has also used [Fe 4 S 4 ] clusters to design well-defined crystalline coordination polymers (CPs) with [Fe 4 S 4 ] clusters and 1,4-benzenedithiolate (BDT). , Importantly, this 1D coordination polymer, [(Fe 4 S 4 )(BDT) 2 ][TMA] 2 ( Fe CP , TMA = tetramethylammonium), is soluble in dimethylformamide (DMF) which suggests that solution processing should be possible, for instance with drop-casting onto an electrode.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic, Spectroscopic, and Theoretical Studies of Fe₄S₄-Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Jiang,

Darù,

Kunstelj

et al. 2024

J. Am. Chem. Soc.

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Iron−sulfur clusters play essential roles in biological systems, and thus synthetic [Fe 4 S 4 ] clusters have been an area of active research. Recent studies have demonstrated that soluble [Fe 4 S 4 ] clusters can serve as net H atom transfer mediators, improving the activity and selectivity of a homogeneous Mn CO 2 reduction catalyst. Here, we demonstrate that incorporating these [Fe 4 S 4 ] clusters into a coordination polymer enables heterogeneous H atom transfer from an electrode surface to a Mn complex dissolved in solution. A previously reported solution-processable Fe 4 S 4 -based coordination polymer was successfully deposited on the surfaces of different electrodes. The coated electrodes serve as H atom transfer mediators to a soluble Mn CO 2 reduction catalyst displaying good product selectivity for formic acid. Furthermore, these electrodes are recyclable with a minimal decrease in activity after multiple catalytic cycles. The heterogenization of the mediator also enables the characterization of solution-phase and electrode surface species separately. Surface enhanced infrared absorption spectroscopy (SEIRAS) reveals spectroscopic signatures for an in situ generated active Mn−H species, providing a more complete mechanistic picture for this system. The active species, reaction mechanism, and the protonation sites on the [Fe 4 S 4 ] clusters were further confirmed by density functional theory calculations. The observed H atom transfer reactivity of these coordination polymer-coated electrodes motivates additional applications of this composite material in reductive H atom transfer electrocatalysis.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Catalytic, Spectroscopic, and Theoretical Studies of Fe₄S₄-Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Jiang,

Darù,

Kunstelj

et al. 2024

J. Am. Chem. Soc.

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Multi‐Scale Design of Metal–Organic Framework Metamaterials for Broad‐Band Microwave Absorption

Qu,

Xu,

Liu

et al. 2024

Adv Funct Materials

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The development of nanocomposite microwave absorbers is a critical strategy for tackling electromagnetic pollution. However, challenges persist regarding material stability and achieving broadband absorption. Herein, a novel multi−scale design approach for metamaterial absorbers is proposed. First, a series of bimetallic (cobalt and copper) semiconductive metal–organic framework (SC−MOF) crystals with atomically resolved structures are successfully prepared to serve as building blocks for metamaterials. By simply adjusting the concentration ratio of the two ions, the controllable preparation of crystal morphology can be achieved. This enables to precisely tune the absorption peak and bandwidth range of the SC−MOF, resulting in excellent EMW absorption performance (effective absorption bandwidth: 6.16 GHz, minimum reflection loss: −61 dB). Based on this, printable inks are further constructed by encapsulating the SC−MOF in polydimethylsiloxane and 3D‐printed multi−layered metamaterial absorbers based on woodpile porous architecture. The metamaterial absorber demonstrates a near‐perfect absorption in the microwave spectrum (with a bandwidth of 11.33 GHz), closely matching theoretical simulations. This multi−scale design approach, combining precise MOF materials construction with topological structure design, offers new insights for the development of broadband microwave absorbers.

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Introducing Metal-Sulfur Active Sites in Metal-Organic Frameworks via Post-Synthetic Modification for Hydrogenation Catalysis

Farha,

Xie,

Khoshooei

et al. 2024

Preprint

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Metal sulfide binary compounds, renowned for their exceptional electronic properties, are advantageous in applications such as hydrogenation, dehydrogenation, and photocatalysis. Typically, the majority of active sites in these compounds reside on the surfaces and edges of catalyst particles, leaving the bulk catalyst underutilized. This study introduces a strategy to embed metal-sulfur active sites into metal-organic frameworks (MOFs) via post-synthetic modification, exploiting the MOFs’ accessible internal surfaces. Two MOF systems, including M2Cl2(BBTA) (H2BBTA = 1H,5H-benzo(1,2-d:4,5-d')bistriazole, M = Co, Ni), which features one-dimensional M–Cl chains and hexagonal channels, and M-MFU-4l-Cl (M = Co, Ni), which contains discrete ZnM4 metal nodes, were selected as starting materials. The conversion processes, from M2Cl2(BBTA) to M2(SH)2(BBTA) and from M-MFU-4l-Cl to M-MFU-4l-SH, were executed through a two-step post-synthetic modification protocol and confirmed by single-crystal XRD, PXRD, PDF, SEM, XPS, and N2 sorption techniques. Catalytic performance was assessed using the reduction of 4-nitrophenol to 4-aminophenol with molecular hydrogen as a model reaction, and significant improvement in performance was observed upon introduction of the SH groups. Density functional theory calculations suggest that the flexibility of the sulfur moiety is crucial in the M–X bond cleavage pathway, enhancing hydrogen activation. This study underscores the efficacy of post-synthetic modification in developing advanced MOF-based catalysts with superior performance for selective hydrogenation reactions, highlighting the strategic advantage of incorporating polarizable sulfur components within MOFs.

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Electrically conductive [Fe₄S₄]-based organometallic polymers

Abstract: Covalent metal-linker bonds greatly enhance the conductivity of hybrid organic–inorganic materials.

Cited by 3 publications

References 52 publications

Catalytic, Spectroscopic, and Theoretical Studies of Fe₄S₄-Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Catalytic, Spectroscopic, and Theoretical Studies of Fe₄S₄-Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Multi‐Scale Design of Metal–Organic Framework Metamaterials for Broad‐Band Microwave Absorption

Introducing Metal-Sulfur Active Sites in Metal-Organic Frameworks via Post-Synthetic Modification for Hydrogenation Catalysis

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Electrically conductive [Fe4S4]-based organometallic polymers

Abstract: Covalent metal-linker bonds greatly enhance the conductivity of hybrid organic–inorganic materials.

Cited by 3 publications

References 52 publications

Catalytic, Spectroscopic, and Theoretical Studies of Fe4S4-Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Catalytic, Spectroscopic, and Theoretical Studies of Fe4S4-Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Multi‐Scale Design of Metal–Organic Framework Metamaterials for Broad‐Band Microwave Absorption

Introducing Metal-Sulfur Active Sites in Metal-Organic Frameworks via Post-Synthetic Modification for Hydrogenation Catalysis

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Product

Resources

About

Electrically conductive [Fe₄S₄]-based organometallic polymers

Catalytic, Spectroscopic, and Theoretical Studies of Fe₄S₄-Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Catalytic, Spectroscopic, and Theoretical Studies of Fe₄S₄-Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis