5 research outputs found
On-surface synthesis of a dicationic diazahexabenzocoronene derivative on the Au(111) surface
The atomically precise control over the size, shape and structure of nanographenes (NGs) or the introduction of heteroatom dopants into their sp2-carbon lattice confer them valuable electronic, optical and magnetic properties. Herein, we report on the design and synthesis of a hexabenzocoronene derivative embedded with graphitic nitrogen in its honeycomb lattice, achieved via on-surface assisted cyclodehydrogenation on the Au(111) surface. Combined scanning tunnelling microscopy/spectroscopy and non-contact atomic force microscopy investigations unveil the chemical and electronic structures of the obtained dicationic NG. Kelvin probe force microscopy measurements reveal a considerable variation of the local contact potential difference toward lower values with respect to the gold surface, indicative of its positive net charge. Altogether, we introduce the concept of cationic nitrogen doping of NGs on surfaces, opening new avenues for the design of novel carbon nanostructure
Resolving AtomicâScale Defects in Conjugated Polymers OnâSurfaces
Atomic scale defects significantly affect the mechanical, electronic, and optical properties of Ï-conjugated polymers. Here, isolated atomic-scale defects are deliberately introduced into a prototypical anthracene-ethynylene Ï-conjugated polymer, and its local density of states is carefully examined on the atomic scale to show how individual defects modify the inherent electronic and magnetic properties of this one-dimensional systems. Scanning tunneling and atomic force microscopy experiments, supplemented with density functional theory calculations, reveal the existence of a sharp electronic resonance at the Fermi energy around certain defects, which is associated with the formation of a local magnetic moment accompanied by substantial mitigation of the mobility of charge carriers. While defects in traditionally synthesized polymers lead to arbitrary conformations, the presented results clearly reflect the preferential formation of low dimensional defects at specific polymer sites, which may introduce the possibility of engineering macroscopic defects in surface-synthesized conjugated polymers.European Regional Development FundComunidad de MadridMinisterio de Ciencia, InnovaciĂłn y UniversidadesMINECODepto. de QuĂmica OrgĂĄnicaFac. de Ciencias QuĂmicasTRUEpu
Tailoring topological order and Ï-conjugation to engineer quasi-metallic polymers
Depto. de QuĂmica OrgĂĄnicaFac. de Ciencias QuĂmicasTRUEpu
Tailoring Ï-conjugation and vibrational modes to steer on-surface synthesis of pentalene-bridged ladder polymers
The development of synthetic strategies to engineer Ï-conjugated polymers is of paramount importance in modern chemistry and materials science. Here we introduce a synthetic protocol based on the search for specific vibrational modes through an appropriate tailoring of the Ï-conjugation of the precursors, in order to increase the attempt frequency of a chemical reaction. First, we design a 1D Ï-conjugated polymer on Au(111), which is based on bisanthene monomers linked by cumulene bridges that tune specific vibrational modes. In a second step, upon further annealing, such vibrational modes steer the twofold cyclization reaction between adjacent bisanthene moieties, which gives rise to a long pentalene-bridged conjugated ladder polymer featuring a low bandgap. In addition, high resolution atomic force microscopy allows us to identify by atomistic insights the resonance form of the polymer, thus confirming the validity of the Glidewell and LloydÂŽs rules for aromaticity. This on-surface synthetic strategy may stimulate exploiting previously precluded reactions towards Ï-conjugated polymers with specific structures and properties.QUIMTRONIC-CM (Y2018/NMT-4783)CTQ2017-83531-RRED2018-102815-T)Comunidad de MadridMINECODepto. de QuĂmica OrgĂĄnicaFac. de Ciencias QuĂmicasTRUEpu