Facile Synthesis of [Cu(SCH₃)]_∞ Nanowires with High Charge Mobility

Abstract

[Cu(SCH3)]∞ nanowires with lengths on the order of hundreds of micrometers were obtained with a facile method from the reaction of Cu(NO3)2⋅3 H2O, dimethyl sulfoxide (DMSO), and water under hydrothermal conditions within a large range of DMSO/water ratios and at various temperatures. These highly crystalline, thermally stable (under vacuum) nanowires are p‐type conducting and have a hole mobility as high as 2 cm2 V−1 S−1, which is 102–105 times higher than previously reported values. The high hole mobility may demonstrate their promising future in various electronic‐device applications.

Reversible Thermochromic Polymeric Thin Films Made of Ultrathin 2D Crystals of Coordination Polymers Based on Copper(I)‐Thiophenolates

“…1 and 2 are almost isostructural to previously reported compound [CuHT] n [7b] (HT = 4‐hydroxy‐thiophenolate). They consists of layers based on fused Cu 3 S 3 rings with the copper atoms adopting a slightly distorted trigonal planar geometry with three μ 3 ‐bridging S atoms of the thiolate ligands showing SCuS bond angles in the range of 103°–130° ( Figures and , Table 1 ).…”

“…Note here that the synthesis of 1 , as micropowder, was also reported by refluxing Cu 2 O and 4‐mba in ethanol. [7c] By replacing acetone by MeOH as the reaction media, we found the formation of polycrystalline [CuMCT] n ( 2 ) due to the in situ esterification of the carboxylic group of 4‐mba (Figures S1 and S2, Supporting Information). This esterification was confirmed by elemental analysis and Fourier transform infrared (FTIR) spectroscopy (Figures S3 and S4, Supporting Information).…”

“…The CuS distances are in the range of 2.24–2.30 Å, which are comparable with those of neutral polymeric homoleptic [Cu(SPh‐ p ‐X)] n (X = H, CH 3 , OCH 3 , NO 2 , OH) (2.24–2.35 Å). [7b,c] These layers are completed by the functionalized phenyl moieties placed above and below the layer. However, the presence of different functional groups in the phenyl ring induces significant modifications in the Cu 3 S 3 rings conformation (half‐chair for 1 vs twist‐boat for 2 ), the thickness of the inorganic core of the 2D sheet (2.037 vs 2.163 Å), the dihedral angle between the phenyl rings inside the sheet (parallel vs 50°), and the supramolecular interactions that held together the layers (hydrogen bonding vs weak van der Waals interactions).…”

“…Overall, the lamellar structures of 1 and 2 are rather unusual since with the exception of the already mentioned [CuHT] n , the only single crystals so far reported are a series of [Cu( p ‐SC 6 H 4 ‐X)] n (X = CH 3 , H, CH 3 O, NO 2 )[7c] showing extended ladder‐like [CuS] chains. In fact, the hexagonal bidimensional networks found in 1 and 2 based on Cu 3 S 3 fused rings structurally resemble to a single layer of β‐phase antimony .…”

“…In particular, those CPs based on Cu(I) seem to be appropriate because of their wide structural variety combined with brightly luminescence emission varying from blue to red light . A specific type of robust CPs is built up from thiolates, which those made of Cu(I), [Cu(SR)] n (SR = thiolate), which have recently shown interesting electrical and/or optical properties . However, examples of Cu(I)‐CPs based on thiolate ligands with thermochromic properties are still very scarce…”