Milani, Alberto Tommasini, Matteo Barbieri, Valentino Lucotti, Andrea Russo, Valeria Cataldo, Franco Casari, Carlo S. Semiconductor-to-Metal Transition in Carbon-Atom Wires Driven by sp<sup>2</sup> Conjugated End Groups Bis­(biphenyl)-capped polyynes are investigated to unveil the modulation of the electronic and optical properties of sp-hybridized carbon-atom wires (CAWs) capped with π-conjugated sp<sup>2</sup> end groups. Raman and surface enhanced Raman spectroscopy experiments and density functional theory (DFT) calculations reveal structural changes from polyyne-like with alternating single–triple bonds toward cumulene-like with more equalized bonds as a consequence of the charge transfer occurring when wires interact with metallic nanoparticles. While polyynes have semiconducting electronic properties, a more equalized system tends to a cumulene-like structure characterized by a nearly metallic behavior. The effect of different sp<sup>2</sup> end groups in driving a semiconductor-to-metal transition is investigated by DFT calculations on a series of CAWs capped with different terminations. We discuss how the modulation of the structural, electronic, and vibrational properties of the sp-carbon chain toward the metallic wire is not trivial and requires a suitable chemical design of the end group and control of charge transfer. These results provide a guideline for the design of novel sp–sp<sup>2</sup> hybrid carbon nanosystems with tunable properties, where graphene-like and polyyne-like domains are closely interconnected. The capability to tune the final electronic or optical response of the material makes these hybrid sp–sp<sup>2</sup> systems appealing for a future all-carbon-based science and technology. sp-hybridized carbon-atom wires;equalized;charge transfer;cumulene-like;Raman spectroscopy experiments;sp 2 end groups;polyyne-like;polyyne;bond;future all-carbon-based science;DFT;calculation;CAW;modulation 2017-04-24
    https://acs.figshare.com/articles/journal_contribution/Semiconductor-to-Metal_Transition_in_Carbon-Atom_Wires_Driven_by_sp_sup_2_sup_Conjugated_End_Groups/4982942
10.1021/acs.jpcc.7b02246.s001