Homocoupling of terminal alkynes on calcite (10.4)

Richter A, Vilas-Varela M, Peña D, Bechstein R, Kühnle A. Homocoupling of terminal alkynes on calcite (10.4). Surface Science. 2018;678:106-111

Molecular bridge engineering for tuning quantum electronic transport and anisotropy in nanoporous graphene

Recent advances on surface-assisted synthesis have demonstrated that arrays of nanometer wide graphene nanoribbons can be laterally coupled with atomic precision to give rise to a highly anisotropic nanoporous graphene structure. Electronically, this graphene nanoarchitecture can be conceived as a set of weakly coupled semiconducting 1D nanochannels with electron propagation characterized by substantial interchannel quantum interferences. Here, we report the synthesis of a new nanoporous graphene structure where the interribbon electronic coupling can be controlled by the different degrees of freedom provided by phenylene bridges that couple the conducting channels. This versatility arises from the multiplicity of phenylene cross-coupling configurations, which provides a robust chemical knob, and from the interphenyl twist angle that acts as a fine-tunable knob. The twist angle is significantly altered by the interaction with the substrate, as confirmed by a combined bond-resolved scanning tunneling microscopy (STM) and ab initio analysis, and should accordingly be addressable by other external stimuli. Electron propagation simulations demonstrate the capability of either switching on/off or modulating the interribbon coupling by the corresponding use of the chemical or the conformational knob. Molecular bridges therefore emerge as efficient tools to engineer quantum transport and anisotropy in carbon-based 2D nanoarchitectures.This research was funded by the CERCA Programme/ Generalitat de Catalunya and by Grant Nos. SEV-2017-0706, CEX2021-001214-S, PID2019-107338RB-C62, PID2019- 107338RB-C65, and PID2019-107338RB-C66 funded by MCIN/AEI/10.13039/501100011033; FLAG-ERA Grant LEGOCHIP Projects PCI2019-111890-2 and PCI2019-111933-2 funded by MCIN/AEI/10.13039/501100011033 and cofunded by the European Union; Grant Nos. TED2021- 132388B-C41, TED2021-132388B-C42, and TED2021- 132388B-C44 funded by MCIN/AEI/10.13039/ 501100011033 and the European Union NextGenerationEU/ PRTR; Xunta de Galicia (Centro de Investigación de Galicia accreditation 2019−2022, ED431G 2019/03). X.D.C., A.S., and A.G.-L. also acknowledge the financial support received from the IKUR Strategy under the collaboration agreement between Ikerbasque Foundation and DIPC on behalf of the Department of Education of the Basque Government. C.M. was supported by Grant RYC2019-028110-I funded by MICIN/AEI/10.13039/501100011033 and by the European Social Fund “ESF Investing in your future”. M.T. was supported by Grant No. BES-2017-08078 funded by MCIN/ AEI/10.13039/501100011033 and by “ESF Investing in your future”. M.B. acknowledges funding from Villum fonden (VIL 00013340)

Survival of spin state in magnetic porphyrins contacted by graphene nanoribbons

We report on the construction and magnetic characterization of a fully functional hybrid molecular system composed of a single magnetic porphyrin molecule bonded to graphene nanoribbons with atomically precise contacts. We use on-surface synthesis to direct the hybrid creation by combining two molecular precursors on a gold surface. High-resolution imaging with a scanning tunneling microscope finds that the porphyrin core fuses into the graphene nanoribbons through the formation of new carbon rings at chemically predefined positions. These ensure the stability of the hybrid and the extension of the conjugated character of the ribbon into the molecule. By means of inelastic tunneling spectroscopy, we prove the survival of the magnetic functionality of the contacted porphyrin. The molecular spin appears unaffected by the graphenoid electrodes, and we simply observe that the magnetic anisotropy appears modified depending on the precise structure of the contacts.We acknowledge the financial support from Spanish Agencia Estatal de Investigación (AEI) (project nos. MAT2016-78293-C6 and FIS2015-62538-ERC, and the Maria de Maeztu Units of Excellence Programme MDM-2016-0618), the Basque Government (Department Industry, grant no. PI-2015-1-42), the European project PAMS (610446), the Xunta de Galicia (Centro singular de investigación de Galicia accreditation 2016 to 2019, ED431G/09), the European Research Council (grant agreement no. 635919), and the European Regional Development FundS

Stabilizing edge fluorination in graphene nanoribbons

The on-surface synthesis of edge-functionalized graphene nanoribbons (GNRs) is challenged by the stability of the functional groups throughout the thermal reaction steps of the synthetic pathway. Edge fluorination is a particularly critical case in which the interaction with the catalytic substrate and intermediate products can induce the complete cleavage of the otherwise strong C-F bonds before the formation of the GNR. Here, we demonstrate how a rational design of the precursor can stabilize the functional group, enabling the synthesis of edge-fluorinated GNRs. The survival of the functionalization is demonstrated by tracking the structural and chemical transformations occurring at each reaction step with complementary X-ray photoelectron spectroscopy and scanning tunneling microscopy measurements. In contrast to previous attempts, we find that the C-F bond survives the cyclodehydrogenation of the intermediate polymers, leaving a thermal window where GNRs withhold more than 80% of the fluorine atoms. We attribute this enhanced stability of the C-F bond to the particular structure of our precursor, which prevents the cleavage of the C-F bond by avoiding interaction with the residual hydrogen originated in the cyclodehydrogenation. This structural protection of the linking bond could be implemented in the synthesis of other sp2-functionalized GNRs

Doping of graphene nanoribbons via functional group edge modification

We report the on-surface synthesis of 7-armchair graphene nanoribbons (7-AGNRs) substituted with nitrile (CN) functional groups. The CN groups are attached to the GNR backbone by modifying the 7-AGNR precursor. Whereas many of these groups survive the on-surface synthesis, the reaction process causes the cleavage of some CN from the ribbon backbone and the on-surface cycloisomerization of few nitriles onto pyridine rings. Scanning tunneling spectroscopy and density functional theory reveal that CN groups behave as very efficient n-dopants, significantly downshifting the bands of the ribbon and introducing deep impurity levels associated with the nitrogen electron lone pairs.This work was supported by FP7 FET-ICT “Planar Atomic and Molecular Scale devices” (PAMS) project (funded by the European Commission under Contract No. 610446), by the Agencia Estatal de Investigacion (Cooperative Grant No. MAT2016-78293 and Grant FIS2015-62538-ERC), the Basque Government (Dep. de Educacion and UPV/EHU, Grant No. IT-756-13, and Dep. Industry, Grant PI_2015_1_42), the Xunta de Galicia (Centro singular de investigacion de Galicia accreditation 2016−2019, ED431G/09), and the European Regional Development Fund (ERDF).Peer Reviewe

Unraveling the electronic structure of narrow atomically precise chiral graphene nanoribbons

This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposesRecent advances in graphene-nanoribbon-based research have demonstrated the controlled synthesis of chiral graphene nanoribbons (chGNRs) with atomic precision using strategies of on-surface chemistry. However, their electronic characterization, including typical figures of merit like band gap or frontier band's effective mass, has not yet been reported. We provide a detailed characterization of (3,1)-chGNRs on Au(111). The structure and epitaxy, as well as the electronic band structure of the ribbons, are analyzed by means of scanning tunneling microscopy and spectroscopy, angle-resolved photoemission, and density functional theoryThe project leading to this publication has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement no. 635919), from the Spanish Ministry of Economy, Industry and Competitiveness (MINECO, grant nos. MAT2016-78293-C6, FIS2015-62538-ERC), from the Basque Government (grant nos. IT-621-13, PI-2015-1-42, PI-2016-1-0027), from the European Commission in FP7 FET-ICT “Planar Atomic and Molecular Scale Devices” (PAMS) project (contract no. 610446), from the Xunta de Galicia (Centro singular de investigación de Galicia accreditation 2016−2019, ED431G/09), and from the European Regional Development Fund (ERDF

Tunable Band Alignment with Unperturbed Carrier Mobility of On-Surface Synthesized Organic Semiconducting Wires

The tunable properties of molecular materials place them among the favorites for a variety of future generation devices. In addition, to maintain the current trend of miniaturisation of those devices, a departure from the present top-down production methods may soon be required and self-assembly appears among the most promising alternatives. On-surface synthesis unites the promises of molecular materials and of self assembly, with the sturdiness of covalently bonded structures: an ideal scenario for future applications. Following this idea, we report the synthesis of functional extended nanowires by self-assembly. In particular, the products correspond to one-dimensional organic semiconductors. The uniaxial alignment provided by our substrate templates allows us to access with exquisite detail their electronic properties, including the full valence band dispersion, by combining local probes with spatial averaging techniques. We show how, by selectively doping the molecular precursors, the product\u2019s energy level alignment can be tuned without compromising the charge carrier\u2019s mobility