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Rsc.Li/Chemical-Science Chemical Science Chemical Science View Article Online EDGE ARTICLE View Journal On-surface synthesis of organocopper metallacycles through activation of inner Cite this: DOI: 10.1039/d1sc03703j † All publication charges for this article diacetylene moieties have been paid for by the Royal Society a b c ad of Chemistry Borja Cirera, Alexander Riss, Pingo Mutombo, Jose´ I. Urgel, ae df d dg Jose´ Santos, Marco Di Giovannantonio, Roland Widmer, Samuel Stolz, d d dh c b Qiang Sun, Max Bommert, Roman Fasel, Pavel Jel´ınek,* Willi Auwarter,¨ * ae a Nazario Mart´ın * and David Ecija´ * The design of organometallic complexes is at the heart of modern organic chemistry and catalysis. Recently, on-surface synthesis has emerged as a disruptive paradigm to design previously precluded compounds and nanomaterials. Despite these advances, the field of organometallic chemistry on surfaces is still at its infancy. Here, we introduce a protocol to activate the inner diacetylene moieties of a molecular precursor by copper surface adatoms affording the formation of unprecedented Creative Commons Attribution-NonCommercial 3.0 Unported Licence. organocopper metallacycles on Cu(111). The chemical structure of the resulting complexes is Received 7th July 2021 characterized by scanning probe microscopy and X-ray photoelectron spectroscopy, being Accepted 28th August 2021 complemented by density functional theory calculations and scanning probe microscopy simulations. DOI: 10.1039/d1sc03703j Our results pave avenues to the engineering of organometallic compounds and steer the development rsc.li/chemical-science of polyyne chemistry on surfaces. Introduction access to surface science techniques to explore materials with utmost spatial resolution.2–6 This article is licensed under a Organocopper compounds play a pivotal role in organic By taking advantage of this novel synthetic paradigm, orga- synthesis, for instance in conjugate addition reactions and nocopper complexes have been designed by exploiting halogen- couplings with sp2 carbons, while also promoting epoxide substituted compounds, typically as intermediates of the Ull- openings, S 2 and S 20 reactions, and alkyne additions, just to mann coupling reaction. Most of the focus has been centered on Open Access Article. Published on 30 August 2021. Downloaded 9/29/2021 9:29:47 AM. N N name a few. Notably, based on this chemical relevance, the halogenated sp2 carbons, with scarce examples reporting the demand for organocopper complexes is increasing due to the formation of organometallic polyyne nanostructures via the low cost and environmental friendliness of copper.1 chemical reactions of brominated or hydrogenated sp – Recently, on-surface synthesis has emerged as a discipline carbons.7 12 that allows the design of chemical products, while providing In parallel, terminal acetylene on-surface chemistry has shown promising results towards the fabrication of well-dened 2,6 aIMDEA Nanoscience, C/Faraday 9, Campus de Cantoblanco, 28049 Madrid, Spain. low-dimensional nanomaterials, illustrating distinct reac- 13–15 16,17 E-mail: [email protected] tions such as Glaser coupling, head to head addition, 18,19 20,21 bPhysics Department E20, Technical University of Munich, D-85748 Garching, alkyne cyclotrimerization, Bergmann reaction, azide– Germany. E-mail: [email protected] alkyne cycloaddition,22,23 Sonogashira coupling24,25 and dehalo- cInstitute of Physics of the Czech Academy of Science, 16253 Praha, Czech Republic. genative homocoupling.26 E-mail: [email protected] Inspired by this previous knowledge, here we introduce dEmpa, Swiss Federal Laboratories for Materials Science and Technology, 8600 a new pathway to activate inner polyyne moieties affording the Dubendorf,¨ Switzerland eDepartamento de Qu´ımica Organica,´ Facultad de Ciencias Qu´ımicas, Universidad formation of unprecedented organocopper metallacycles. To Complutense de Madrid, 28040 Madrid, Spain. E-mail: [email protected] this aim we deposit the precursor 1,4-di(naphthalen-2-yl)butadi- fIstituto di Struttura della Materia – CNR (ISM-CNR), via Fosso del Cavaliere 100, 1,3-yne (1), termed DNBD, on Cu(111) held at room tempera- 00133 Roma, Italy ture. Such species incorporate an inner 1,3-butadiyne moiety gInstitute of Physics, Ecole´ Polytechnique F´ed´erale de Lausanne, CH-1015 Lausanne, that is connected at both termini to rotatable naphthalene Switzerland moieties. Our scanning probe microscopy (SPM) study com- hDepartment of Chemistry, Biochemistry and Pharmaceutical Sciences, University of plemented by X-ray photoelectron spectroscopy (XPS), density Bern, 3012 Bern, Switzerland † Electronic supplementary information (ESI) available. See DOI: functional theory (DFT) and scanning probe microscopy calcu- 10.1039/d1sc03703j lations reveals that the two exterior carbon atoms of the © 2021 The Author(s). Published by the Royal Society of Chemistry Chem. Sci. View Article Online Chemical Science Edge Article diacetylene skeleton of DNBD are attacked by copper adatoms a mechanism by which the inner triple bonds of the diacetylene resulting in the synthesis of organocopper metallacycles, bridges react with copper adatoms. The organometallic through the transformation of the diacetylene moiety of the complexes can adopt six different conformations (cf. Fig. 2c–h), precursors into a cumulene-like structure. Our results pave with associated chiral ones with respect to the substrate. As avenues for the activation of carbons on metal surfaces, giving depicted in the histogram in Fig. 2i, three conformers occur rise to the design of unique organometallic complexes of much more frequently. Notably, the longitudinal axis of potential relevance for modern organic synthesis and catalysis. symmetry of the macrocycle is aligned with the close-packed directions of Cu(111). The robustness of the organocopper metallacycles is conrmed by performing lateral manipulation, Results and discussion revealing that the complexes can be displaced and rotated along The synthesis of molecular species 1 (cf. the le panel of Fig. 1a the surface over long distances (cf. Fig. 2j and k). In addition, and S1† for synthetic details) was conceived to equip a diac- a scanning probe microscopy image acquired at 77 K shows that ff etylene moiety with protecting naphthalene units at its termini, they di use as a whole along the close-packed directions of the which are able to rotate through a single bond, thus featuring two surface (cf. Fig. 2l). Such ndings corroborate the formation of – – conformers upon adsorption, named s-cis and s-trans (cf. the le two relatively strong C Cu C bonds per organometallic panel of Fig. 1a). Thanks to that geometrical exibility we envi- complex. sioned that the carbon atoms involved in the butadiene bridge In order to get more information about the chemical could be easily attacked by metal adatoms on specic coinage structure of the organocopper metallacycle, we performed surfaces (cf. the right panel of Fig. 1a). To this aim, the behavior of high-resolution X-ray photoelectron spectroscopy (HR-XPS) the molecular precursor was inspected on surfaces with low and using synchrotron radiation as the photon source. The C 1s high reactivity, i.e., Au(111) and Cu(111), respectively. core level of a sample with a coverage of 0.4 ML is shown in First, the deposition of DNBD on Au(111) held at room Fig. 2m. The carbon atoms contained in complex 2 appear in ff Creative Commons Attribution-NonCommercial 3.0 Unported Licence. temperature results in the formation of chain-like nano- di erent chemical environments: 4 are bound to Cu adatoms, 4 constitute the cumulene bridges (with sp hybridization), 12 are structures that evolve towards a closely packed assembly upon 2 high coverage, stabilized through van der Waals interactions (cf. connected to other carbon atoms only, with sp hybridization, the le panel of Fig. 1b and S2a–d†). Importantly, high resolu- and 28 are linked to hydrogens. Deconvolution of the C 1s tion images allow us to discern the intact species featuring s-cis signal has been performed by xing these relative ratios, which or s-trans isomers, whereas the s-trans is in the majority (>90%). produces the t reported in Fig. 2m that is in very good Consecutive annealing steps up to 650 K give rise to the agreement with the experimental data. The components – – 2 formation of irregularly polymerized species, signaling uncon- related to C HandCCinthesp hybridized moieties (blue trolled reaction pathways (cf. Fig. S2e and f†). and green lled curves in Fig. 2m) appear at 284.1 eV and This article is licensed under a 27 The above mentioned scenario changes dramatically when 284.6 eV, respectively, while the carbon atoms in the sp DNBD is deposited on the more reactive Cu(111) held at room cumulene moieties (orange lled curve in Fig. 2m) display temperature. As illustrated in Fig. 2, a submonolayer coverage a spectroscopic signal at higher binding energy (285.1 eV). It Open Access Article. Published on 30 August 2021. Downloaded 9/29/2021 9:29:47 AM. results in the expression of cross-like entities (cf. right panel of must be noted that a t without a separate component arising Fig. 1b, 2a and b) which are visualized in constant-current STM from the sp cumulene moieties did not satisfactorily reproduce † as two central lobes surrounded by four elongated protrusions, the experimental data (see Fig. S3 ). Interestingly, the compo- which can have distinct relative orientations. Such entities are nent at lower binding energy (283.5 eV, purple lled curve in rationalized as cumulene-based organocopper metallacycles (2), Fig. 2m) con rms the presence of metal-bound carbon atoms, 27,28 the formation of which is tentatively explained thanks to as previously reported. Fig. 1 Conformations, self-assembly and transformations of DNBD species on Au(111) and Cu(111). (a) Chemical scheme of the DNBD conformers (1) and organocopper metallacycles (2). (b) High resolution STM image of the DNBD conformers on Au(111) and the organometallic cycles (2) on Cu(111). Au(111): It ¼ 120 pA, Vb ¼0.25 V, scale bar ¼ 1 nm; Cu(111): It ¼ 500 pA, Vb ¼1.5 V, scale bar ¼ 1nm.
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