Highly Conductive Organic–Inorganic Hybrid Silver Sulfide with 3D Silver–Sulfur Networks Constructed from Benzenehexathiol: Structural Topology Regulation via Ligand Oxidation

Abstract

Construction of conductive coordination polymers (CPs) has already become an attractive strategy for the development of organic− inorganic hybrid functional materials with specific electrical performance, due to the great diversity and tunability of the chemical structures, electronic structures, as well as the functions they can offer. Here, we demonstrate a novel highly conductive CP based on silver (I) and benzenehexathiol (BHT), (Ag 3 BHT) n , which displays a different chemical stoichiometry and structural topology compared to the previously reported (Ag 5 BHT) n . Detailed structural analysis shows that this is caused by the unintentional oxidation of the ligand molecules during the CP formation process. (Ag 3 BHT) n displays an electrical conductivity of 39 S cm −1 at room temperature. Ultraviolet photoelectron spectroscopy characterization and density functional theory calculation reveal that its highly conducting behavior comes from the highly doped character of (Ag 3 BHT) n . In addition, band structure calculation proposed an unusual double Dirac cone. This work emphasizes the importance of the ligand oxidation strategy, which can greatly enrich the family of conductive CPs based on BHT and other noninnocent ligands.

The Recent Development of Two‐dimensional Conjugated Coordination Polymers

“…NH 3 sensor based on Cu 3 BHT films shows a lower detection limit of 0.23 ppm and high selectivity > 30 at an ultra-low drive voltage of 0.01 V compared to other reported 2D c-CPs. These results demonstrate the potential application of 2D c-CPs films as wearable sensors to monitor NH 3 in real-time with low power consumption and long Ni 3 (BHT) hxl 1.4 0.345 5 [35,45] Ag 3 (BHT) hxl 0.877 0.336 39 [24] Cu 3 (BHT) hxl 0.845 0.338 1580 [25] Cu 3 (BHS) hxl 0.896 0.368 110 [14] Ni 3 (HTTP) 2 hcb 2.19 0.33 - [7] Co 3 (HHTP) 2 hcb 2.21 -- [7] Cu 3 (HHTP) 2 hcb --0.21 [7] Ni 3 (HITP) 2 hcb 2.17 0.33 40 [9] Co 3 (HSeTP) Note: hxl = hexagonal lattice, hcb = honeycomb lattice, sql = square lattice c) The I ds versus V gs transfer curves of the device. Reproduced under terms of the CC-BY license [25] Copyright 2015, Springer Nature.…”

“…In 2022, Xu et al. synthesized two analogous 2D c‐CPs of (Ag 3 BHT) n in different solvothermal conditions [24] . By lowering the reaction temperature to −40 °C and replacing ethanol with acetonitrile, the reaction product of BHT with AgNO 3 was shifted from (Ag 5 BHT) n to (Ag 3 BHT) n (Figure 2d).…”

Strain-promoted conductive metal-benzenhexathiolate frameworks for overall water splitting

“…[35] Up to date, some M-BHT frameworks have been successfully synthesized, including Cu-BHT, Fe-BHT, Ag-BHT, and Au-BHT. [35][36][37][38][39] It is noticed that various conductive 2D MOFs have been applied in the field of electrocatalysis. [40][41][42][43] For example, Co3(HITP)2 shows prominent OER activity with the overpotential of 254 mV at 10 mA cm -2 in alkaline electrolyte.…”