Synthesis and charge delocalization property of multimetallic molecular wires with diethynylthiophene bridges

Single-molecule junctions of multinuclear organometallic wires: long-range carrier transport brought about by metal–metal interaction

“…We prepared multinuclear molecular wires 2Py and 3Py in two steps from the known vinylidene complex [ trans -ClRu(dppe) 2 (C CH 2 )][PF 6 ]. 31–34 Treatment of the vinylidene complex with H–C C–Th–C C–H 4 (for 2Py ; Th: 2,5-thiophenediyl) and trans -(H–C C–Th–C C) 2 Ru(dppe) 2 5 (for 3Py ) followed by Sonogashira coupling reaction with 4-bromopyridine afforded 2Py and 3Py , respectively. On the other hand, gold-terminated complexes 2Au and 3Au with N-heterocyclic carbene auxiliaries were prepared via sequential desilylation and auration of the TMS-protected precursors 2TMS and 3TMS , respectively, which were obtained from trans -ClRu(dppe) 2 (C CC CTMS) and 4 / 5 .…”

Synthesis and charge transfer characteristics of a ruthenium–acetylide complex

“…More recently, their charge transfer behaviour was investigated by various methods, including mechanically controllable break junction (MCBJ), where this class of complexes demonstrated high conductivity 1,2 and spectro-electrochemical analysis, in which their redox responsiveness and different charge transfer modes such as metal-toligand charge-transfer (MLCT), ligand-to-metal charge-transfer (LMCT) and even inter valence charge transfer (IVCT) were studied. [3][4][5] Yet while the through-bond charge transfer behaviours were investigated by the above-mentioned methods, their through-space (or inter-molecular) charge transfer ability still remains ambiguous despite of its importance for organic electronic applications. Furthermore, unlike other Ru-compounds, which have been used as dopants for (organic) semiconductors, the doping ability of ruthenium-acetylide complexes is still unclear.…”

Modular Redox Switching of Dinuclear Organometallic Molecular Junctions

“…We have synthesized the diruthenium acetylide complexes 1 R (R = OMe, H, CF3) through coupling between the mononuclear chloro precursor with the SMe-terminated acetylide ligand and appropriate 2,5-disubstituted 1,4diethynylbenzenes in 30-72 % yields in a manner similar to the method reported previously. [24][25][26] The obtained diruthenium complexes 1 R were fully characterized through conventional spectroscopic methods including nuclear magnetic resonance (NMR), infrared and high-resolution mass spectroscopy, and elemental analyses. Single sets of 1 H (Figure 2b) and 31 P{ 1 H} NMR signals (δp ~54 ppm, See SI) indicate highly symmetric structures.…”

“…ν(C≡C) vibration frequencies observed around 2060 cm -1 are comparable to those of the relevant ruthenium acetylides. 24,25 The X-ray structure of 1 H shown in Figure 2c reveals a rigid rod-like structure, and the Ru-Ru and S-S distances were 12.190 and 30.819 Å, respectively. The Ru-C (2.040 Å) and C≡C (1.219 Å) bond lengths are within the ranges of those reported previously.…”