Construction of Conducting Bimetallic Organic Metal Chalcogenides Via Selective Metal Metathesis and Oxidation Transformation

Overview

Journal Nat Commun

Specialty Biology

Date 2022 Oct 22

PMID 36272979

Authors

Yigang Jin

Yuhui Fang

Ze Li

Xiang Hao

Feng He

Bo Guan

Dongwei Wang

Sha Wu

Yang Li

Caiming Liu

Xiaojuan Dai

Ye Zou

Yimeng Sun

Wei Xu

Affiliations

Soon will be listed here.

Abstract

Conducting organic metal chalcogenides (OMCs) have attracted considerable interest for their superior electrical properties and fascinating functions. However, the electronic structural and functional regulation of OMCs are typically limited to the combination of monometallic nodes and graphene-like ligands. Here, we report a family of bimetallic OMCs ([CuAg(CS)], x = 4 or 2) synthesized via selective metal metathesis and oxidation transformation. Both OMCs have alternatively stacked one-dimensional (1D) copper-dithiolene chains and 2D Ag-S networks, which can synergistically serve as charge transport pathways, rendering these bimetallic materials highly conductive. The incorporation of heterometallic nodes turned nonmagnetic [Ag(CS)] into paramagnetic metallic [CuAg(CS)], which exhibited a coherence-incoherence crossover in magnetic susceptibility measurements and an unusually large Sommerfeld coefficient, reminiscent of the characteristics of Kondo lattice. This work opens up an avenue for tailoring the electronic structures of OMCs and provides a platform for studying the dichotomy between electronic localization and itinerancy.

References

Li Y, Jiang X, Fu Z, Huang Q, Wang G, Deng W . Coordination assembly of 2D ordered organic metal chalcogenides with widely tunable electronic band gaps. Nat Commun. 2020; 11(1):261. PMC: 6959344. DOI: 10.1038/s41467-019-14136-8. View

Zhang Y, Lu H, Zhu X, Tan S, Feng W, Liu Q . Emergence of Kondo lattice behavior in a van der Waals itinerant ferromagnet, FeGeTe. Sci Adv. 2018; 4(1):eaao6791. PMC: 5770166. DOI: 10.1126/sciadv.aao6791. View

Idobata Y, Zhou B, Kobayashi A, Kobayashi H . Molecular alloy with diluted magnetic moments-molecular Kondo system. J Am Chem Soc. 2011; 134(2):871-4. DOI: 10.1021/ja210019y. View

Xing G, Li Y, Feng Z, Singh D, Pauly F . Copper(I)-Based Flexible Organic-Inorganic Coordination Polymer and Analogues: High-Power Factor Thermoelectrics. ACS Appl Mater Interfaces. 2020; 12(48):53841-53851. DOI: 10.1021/acsami.0c17148. View

Huang X, Zhang S, Liu L, Yu L, Chen G, Xu W . Superconductivity in a Copper(II)-Based Coordination Polymer with Perfect Kagome Structure. Angew Chem Int Ed Engl. 2017; 57(1):146-150. DOI: 10.1002/anie.201707568. View

Dou J, Sun L, Ge Y, Li W, Hendon C, Li J . Signature of Metallic Behavior in the Metal-Organic Frameworks M(hexaiminobenzene) (M = Ni, Cu). J Am Chem Soc. 2017; 139(39):13608-13611. DOI: 10.1021/jacs.7b07234. View

Duan H, Guo P, Wang C, Tan H, Hu W, Yan W . Beating the exclusion rule against the coexistence of robust luminescence and ferromagnetism in chalcogenide monolayers. Nat Commun. 2019; 10(1):1584. PMC: 6451016. DOI: 10.1038/s41467-019-09531-0. View

Zhao M, Chen B, Xi Y, Zhao Y, Xu H, Zhang H . Kondo Holes in the Two-Dimensional Itinerant Ising Ferromagnet FeGeTe. Nano Lett. 2021; 21(14):6117-6123. DOI: 10.1021/acs.nanolett.1c01661. View

Huang X, Qiu Y, Wang Y, Liu L, Wu X, Liang Y . Highly Conducting Organic-Inorganic Hybrid Copper Sulfides Cu C S (x=4 or 5.5): Ligand-Based Oxidation-Induced Chemical and Electronic Structure Modulation. Angew Chem Int Ed Engl. 2020; 59(50):22602-22609. DOI: 10.1002/anie.202009613. View

10.

Wang M, Dong R, Feng X . Two-dimensional conjugated metal-organic frameworks (2D -MOFs): chemistry and function for MOFtronics. Chem Soc Rev. 2021; 50(4):2764-2793. DOI: 10.1039/d0cs01160f. View

11.

Clough A, Orchanian N, Skelton J, Neer A, Howard S, Downes C . Room Temperature Metallic Conductivity in a Metal-Organic Framework Induced by Oxidation. J Am Chem Soc. 2019; 141(41):16323-16330. DOI: 10.1021/jacs.9b06898. View

12.

Yan H, Hohman J, Li F, Jia C, Solis-Ibarra D, Wu B . Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly. Nat Mater. 2016; 16(3):349-355. DOI: 10.1038/nmat4823. View

13.

Kambe T, Sakamoto R, Kusamoto T, Pal T, Fukui N, Hoshiko K . Redox control and high conductivity of nickel bis(dithiolene) complex π-nanosheet: a potential organic two-dimensional topological insulator. J Am Chem Soc. 2014; 136(41):14357-60. DOI: 10.1021/ja507619d. View

14.

Huang X, Sheng P, Tu Z, Zhang F, Wang J, Geng H . A two-dimensional π-d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour. Nat Commun. 2015; 6:7408. PMC: 4490364. DOI: 10.1038/ncomms8408. View

15.

Tanabe K, Cohen S . Postsynthetic modification of metal-organic frameworks--a progress report. Chem Soc Rev. 2010; 40(2):498-519. DOI: 10.1039/c0cs00031k. View

16.

Yang Y, Fisk Z, Lee H, Thompson J, Pines D . Scaling the Kondo lattice. Nature. 2008; 454(7204):611-3. DOI: 10.1038/nature07157. View

17.

Ananikov V, Orlov N, Zalesskiy S, Beletskaya I, Khrustalev V, Morokuma K . Catalytic adaptive recognition of thiol (SH) and selenol (SeH) groups toward synthesis of functionalized vinyl monomers. J Am Chem Soc. 2012; 134(15):6637-49. DOI: 10.1021/ja210596w. View

18.

Huang X, Li H, Tu Z, Liu L, Wu X, Chen J . Highly Conducting Neutral Coordination Polymer with Infinite Two-Dimensional Silver-Sulfur Networks. J Am Chem Soc. 2018; 140(45):15153-15156. DOI: 10.1021/jacs.8b07921. View

19.

Takenaka T, Ishihara K, Roppongi M, Miao Y, Mizukami Y, Makita T . Strongly correlated superconductivity in a copper-based metal-organic framework with a perfect kagome lattice. Sci Adv. 2021; 7(12). PMC: 7968839. DOI: 10.1126/sciadv.abf3996. View

20.

Urano , Nohara , Kondo , Sakai , Takagi , Shiraki . LiV2O4 spinel as a heavy-mass fermi liquid: anomalous transport and role of geometrical frustration. Phys Rev Lett. 2000; 85(5):1052-5. DOI: 10.1103/PhysRevLett.85.1052. View