0000000000309463
AUTHOR
Julia Ponce
Effect of Metal Complexation on the Conductance of Single-Molecular Wires Measured at Room Temperature
The present work aims to give insight into the effect that metal coordination has on the room-temperature conductance of molecular wires. For that purpose, we have designed a family of rigid, highly conductive ligands functionalized with different terminations (acetylthiols, pyridines, and ethynyl groups), in which the conformational changes induced by metal coordination are negligible. The single-molecule conductance features of this series of molecular wires and their corresponding Cu(I) complexes have been measured in break-junction setups at room temperature. Experimental and theoretical data show that no matter the anchoring group, in all cases metal coordination leads to a shift towar…
Fast Pirouetting Motion in a Pyridine Bisamine-Containing Copper-Complexed Rotaxane
The present work reports the introduction of pyridine bisamine terdentate ligands in the structure of a pirouetting copper rotaxane. Rotaxane 2[PF6] constitutes the first example of the incorporation of imine-based dynamic covalent chemistry in the synthesis of switchable copper-complexed interlocked systems. In this rotaxane, the substitution of the classical terpyridine terdentate unit by a pyridine bisamine moiety has led to a significant stabilization of the pentacoordinated site. That fact has been evidenced by EPR spectroscopy and cyclic voltammetry. Regarding the tetracoordinated site, the congestion around the coordination sphere has been reduced to accelerate the typically slow reo…
Self-assembly of an iron(ii)-based M5L6 metallosupramolecular cage
A pentanuclear M(5)L(6) coordination cage is self-assembled in solution from a rigid linear heteroditopic phen-tpy ligand and an iron (II) salt.
Fast redox-triggered shuttling motions in a copper rotaxane based on a phenanthroline–terpyridine conjugate
Fast shuttling motions in solution have been observed by cyclic voltammetry in a Cu(I/II)-based [2] rotaxane. In the reported system, the different coordination preferences of both copper oxidation states are exploited to promote the electrochemically-triggered gliding of the ring from a tetra to a pentacoordinated site and vice versa. The thread of this rotaxane consists of a tridentate 2,2':6',2''-terpyridine chelating unit directly bonded through its 5-position to the 3-position of the bidentate 1,10-phenanthroline unit. This distribution reduces to a minimum the distance between the two coordination sites and lessens the congestion around the tetrahedral environment. These two factors h…
Photophysical Properties of Oligo(phenylene ethynylene) Iridium(III) Complexes Functionalized with Metal-Anchoring Groups
[EN] The electrochemical and photophysical properties of a family of conjugated ligands and their iridium(III) cyclometallated complexes are described. They consist of a series of monocationic Ir-III bis-2-phenylpyridine complexes with p-phenylethynyl-1,10-phenanthroline ligands of different length. The structure of these ligands includes terminal acetylthiol or pyridine groups, which can provide good electrical contacts between metal electrodes. Cyclic voltammetry, absorption and emission spectroscopy, laser flash photolysis and density functional theory calculations reveal that the high conjugation of the diimine ligand affords small energy gaps between the frontier orbitals. Nevertheless…