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Understanding and controlling isomerization at the single molecular level should provide new insight into the molecular dynamics and design guidelines of functional devices. Scanning tunneling microscopy (STM) has been demonstrated to be a powerful tool to study isomerization of single molecules on a substrate, by either electric field or inelastic electron tunneling mechanisms. A similar molecular isomerization process can in principle be induced by mechanical force; however, relevant study has remained elusive. Here, we demonstrate that isomerization of a N,N-dimethylamino-dianthryl-benzene molecule on Ag(100) can be mechanically driven by the STM tip. The existence of an out-of-plane dimethylamino group in the molecule is found to play a pivotal role in the isomerization process by providing a steric hindrance effect for asymmetric interaction between the STM tip and the molecule. This underlying mechanism is further confirmed by performing molecular dynamics simulations, which show agreement with experimental results. Our work opens the opportunity to manipulate the molecular configuration on the basis of mechanical force.

We report the first bottom‐up synthesis of NBN‐doped zigzag‐edged GNRs (NBN‐ZGNR1 and NBN‐ZGNR2) through surface‐assisted polymerization and cyclodehydrogenation based on two U‐shaped molecular precursors with an NBN unit preinstalled at the zigzag edge. The resultant zigzag‐edge topologies of GNRs are elucidated by high‐resolution scanning tunneling microscopy (STM) in combination with noncontact atomic force microscopy (nc‐AFM). Scanning tunneling spectroscopy (STS) measurements and density functional theory (DFT) calculations reveal that the electronic structures of NBN‐ZGNR1 and NBN‐ZGNR2 are significantly different from those of their corresponding pristine fully‐carbon‐based ZGNRs. Additionally, DFT calculations predict that the electronic structures of NBN‐ZGNRs can be further tailored to be gapless and metallic through one‐electron oxidation of each NBN unit into the corresponding radical cations. This work reported herein provides a feasible strategy for the synthesis of GNRs with stable zigzag edges yet tunable electronic properties., Close to the edge: Two novel NBN‐doped zigzag‐edged graphene nanoribbons (ZGNRs) are derived through surface‐assisted synthesis. Experiments and calculations reveal the importance of the NBN units in modulating the electronic structures of the ZGNRs. Moreover, theoretical calculations predict that the electronic structures of NBN‐ZGNRs can be further tailored through one‐electron oxidation of each NBN unit into the corresponding radical cations.

In this work, we demonstrate the bottom-up on-surface synthesis of poly( para-dibenzo[ bc, kl]-coronenylene) (PPDBC), a zigzag edge-encased analog of poly( para-phenylene) (PPP), and its lateral fusion into zigzag edge-extended graphene nanoribbons (zeeGNRs). Toward this end, we designed a dihalogenated di( meta-xylyl)anthracene monomer displaying strategic methyl groups at the substituted phenyl ring and investigated its applicability as precursor in the thermally induced surface-assisted polymerization and cyclodehydrogenation. The structure of the resulting zigzag edge-rich (70%) polymer PPDBC was unambiguously confirmed by scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). Remarkably, by further thermal treatment at 450 °C two and three aligned PPDBC chains can be laterally fused into expanded zeeGNRs, with a ribbon width of nine ( N = 9) up to 17 ( N = 17) carbon atoms. Moreover, the resulting zeeGNRs exhibit a high ratio of zigzag (67%) vs armchair (25%) edge segments and feature electronic band gaps as low as 0.9 eV according to gaps quasiparticle calculations.

The vast potential of organic materials for electronic, optoelectronic and spintronic devices entails substantial interest in the fabrication of π-conjugated systems with tailored functionality directly at insulating interfaces. On-surface fabrication of such materials on non-metal surfaces remains to be demonstrated with high yield and selectivity. Here we present the synthesis of polyaromatic chains on metallic substrates, insulating layers, and in the solid state. Scanning probe microscopy shows the formation of azaullazine repeating units on Au(111), Ag(111), and h-BN/Cu(111), stemming from intermolecular homo-coupling via cycloaddition reactions of CN-substituted polycyclic aromatic azomethine ylide (PAMY) intermediates followed by subsequent dehydrogenation. Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry demonstrates that the reaction also takes place in the solid state in the absence of any catalyst. Such intermolecular cycloaddition reactions are promising methods for direct synthesis of regioregular polyaromatic polymers on arbitrary insulating surfaces.

A two-dimensional (2D) sp2 -carbon-linked conjugated polymer framework (2D CCP-HATN) has a nitrogen-doped skeleton, a periodical dual-pore structure and high chemical stability. The polymer backbone consists of hexaazatrinaphthalene (HATN) and cyanovinylene units linked entirely by carbon-carbon double bonds. Profiting from the shape-persistent framework of 2D CCP-HATN integrated with the electrochemical redox-active HATN and the robust sp2 carbon-carbon linkage, 2D CCP-HATN hybridized with carbon nanotubes shows a high capacity of 116 mA h g-1 , with high utilization of its redox-active sites and superb cycling stability (91 % after 1000 cycles) and rate capability (82 %, 1.0 A g-1 vs. 0.1 A g-1 ) as an organic cathode material for lithium-ion batteries.

The vast potential of organic materials for electronic, optoelectronic and spintronic devices entails substantial interest in the fabrication of π-conjugated systems with tailored functionality directly at insulating interfaces. On-surface fabrication of such materials on non-metal surfaces remains to be demonstrated with high yield and selectivity. Here we present the synthesis of polyaromatic chains on metallic substrates, insulating layers, and in the solid state. Scanning probe microscopy shows the formation of azaullazine repeating units on Au(111), Ag(111), and h-BN/Cu(111), stemming from intermolecular homo-coupling via cycloaddition reactions of CN-substituted polycyclic aromatic azomethine ylide (PAMY) intermediates followed by subsequent dehydrogenation. Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry demonstrates that the reaction also takes place in the solid state in the absence of any catalyst. Such intermolecular cycloaddition reactions are promising methods for direct synthesis of regioregular polyaromatic polymers on arbitrary insulating surfaces., This work was financially supported by the European Research Council Consolidator Grant NanoSurfs (no. 615233), the Advanced Grant (no. 694097), the Horizon 2020 research and innovation program 2D ink (no. 664878) and the National Science Foundation of China (no. 11974403 and Sino-German Project no. 51761135130). W.A. acknowledges funding by the DFG via a Heisenberg professorship. M.R., R.B., and X.F. thank the German Research Foundation (DFG) within the Cluster of Excellence “Center for Advancing Electronics Dresden (cfaed)” and EnhanceNano (No. 391979941). A.P.P. and A.Ru. thank the Cluster of Excellence "Advanced Imaging of Matter (AIM)" and Grupos Consolidados (IT1249-19). M.G. acknowledges funding by the H2020-MSCA-IF−2014 program under GA no. 658070 (2DNano).

Triangular zigzag nanographenes, such as triangulene and its π‐extended homologues, have received widespread attention as organic nanomagnets for molecular spintronics, and may serve as building blocks for high‐spin networks with long‐range magnetic order, which are of immense fundamental and technological relevance. As a first step towards these lines, we present the on‐surface synthesis and a proof‐of‐principle experimental study of magnetism in covalently bonded triangulene dimers. On‐surface reactions of rationally designed precursor molecules on Au(111) lead to the selective formation of triangulene dimers in which the triangulene units are either directly connected through their minority sublattice atoms, or are separated via a 1,4‐phenylene spacer. The chemical structures of the dimers have been characterized by bond‐resolved scanning tunneling microscopy. Scanning tunneling spectroscopy and inelastic electron tunneling spectroscopy measurements reveal collective singlet–triplet spin excitations in the dimers, demonstrating efficient intertriangulene magnetic coupling., The on‐surface synthesis of covalently bonded triangulene dimers with or without a 1,4‐phenylene spacer was achieved on Au(111). Scanning tunneling spectroscopy measurements revealed collective magnetism in the dimers in the form of singlet–triplet spin excitations, demonstrating efficient and tunable intertriangulene magnetic coupling.

Polycyclic aromatic azomethine ylides (PAMYs) are powerful building blocks in the bottom-up synthesis of internally nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs) through 1,3-cycloaddition reactions. In this work, the cycloaddition reaction of PAMYs to asymmetric ortho-quinones is presented, which, in contrast to the addition to symmetric para-quinones, facilitates subsequent condensation reactions and allows the synthesis of three helical N-PAHs with ullazine-quinoxaline (UQ-1-3) backbones. UQ-1 and UQ-2 possess two helical centers; however, single-crystal X-ray analysis together with the computational modeling of UQ-3 elucidate the formation of only the thermodynamically most stable geometry with four helical centers in a (P,P,M,M) configuration. For the series UQ-1-3, the number of redox steps is directly correlated with the number of ullazine or quinoxaline units incorporated into the targeted molecular backbones. A detailed investigation of the spectroscopic and magnetic properties of the radical cation and anion as well as the dication and dianion species by in situ EPR/UV/Vis-NIR spectroelectrochemistry is provided. The excellent optical and redox properties combined with helical geometries render them possibly applicable as chiral emitter or ambipolar charge transport material in organic electronics.

Herein, we report the design and synthesis of a series of novel cationic nitrogen-doped nanographenes (CNDNs) with nonplanar geometry and axial chirality. Single-crystal X-ray analysis reveals helical and cove-edged structures. Compared to their all-carbon analogues, the frontier orbitals of the CNDNs are energetically lower lying, with a reduced optical energy gap and greater electron-accepting behavior. Cyclic voltammetry shows all the derivatives to undergo quasireversible reductions. In situ spectroelectrochemical studies prove that, depending on the number of nitrogen dopants, either neutral radicals (one nitrogen dopant) or radical cations (two nitrogen dopants) are formed upon reduction. The concept of cationic nitrogen doping and introducing helicity into nanographenes paves the way for the design and synthesis of expanded nanographenes or even graphene nanoribbons with cationic nitrogen dopants.

Synthesis of antiaromatic polycyclic hydrocarbons (PHs) is challenging because the high energy of their highest occupied molecular orbital and low energy of their lowest unoccupied molecular orbital cause them to be reactive and unstable. In this work, two large antiaromatic acene analogues, namely, cyclopenta[pqr]indeno[2,1,7-ijk]tetraphene (CIT, 1a) and cyclopenta[pqr]indeno[7,1,2-cde]picene (CIP, 1b), as well as a curved antiaromatic molecule with 48 π-electrons, dibenzo[a,c]diindeno[7,1,2-fgh:7',1',2'-mno]phenanthro[9,10-k]tetraphene (DPT, 1c), are synthesized on the basis of the corona of indeno[1,2-b]fluorene. These three antiaromatic PHs possess a narrow energy gap down to 1.55 eV and exhibit high kinetic stability under ambient conditions. Moreover, these compounds display reversible electron transfer processes in both the cathodic and anodic regimes. Their cation and anion radicals are characterized by in situ vis-NIR absorption and electron paramagnetic resonance spectroelectrochemistry. The X-ray crystallographic analysis confirms that while CIP and CIT manifest planar structures, DPT shows a curved π-conjugated carbon skeleton. The synthetic strategy starting from ortho-substituted benzene units to construct five-membered rings in this work provides a unique entry to novel pentagon-embedding or curved antiaromatic polycyclic hydrocarbons. In addition, besides the detailed chemical and physical investigations, microscale single-crystal fiber field-effect transistors were also fabricated.

The on-surface reactions of 10-bromo-10'-(2,6-dimethylphenyl)-9,9'-bianthracene on Au(111) surface have been investigated by a combination of bond-resolved scanning tunneling microscopy, scanning tunneling spectroscopy, and tightbinding and mean-field Hubbard calculations. The reactions afford the synthesis of two open-shell nanographenes (1a and 1b) exhibiting different scenarios of all-carbon magnetism. 1a, an allbenzenoid nanographene with previously unreported triangulenelike termini, contains a high proportion of zigzag edges, which endows it with an exceedingly low frontier gap of 110 meV and edge-localized states. The dominant reaction product (1b) is a non-benzenoid nanographene consisting of a single pentagonal ring in a benzenoid framework. The presence of this nonbenzenoid topological defect, which alters the bond connectivity in the hexagonal lattice, results in a non-Kekulé nanographene with a spin S = ½, which is detected as a Kondo resonance. Our work provides evidence of all-carbon magnetism, and motivates the use of topological defects as structural elements toward engineering agnetism in carbon-based nanomaterials for spintronics.

Nanographenes (NGs) have gained increasing attention due to their immense potential as tailor-made organic materials for nanoelectronics and spintronics. They exhibit a rich spectrum of physicochemical properties that can be tuned by controlling the size or the edge structure or by introducing structural defects in the honeycomb lattice. Here, we report the design and on-surface synthesis of NGs containing several odd-membered polycycles induced by a thermal procedure on Au(111). Our scanning tunneling microscopy, noncontact atomic force microscopy, and scanning tunneling spectroscopy measurements, complemented by computational investigations, describe the formation of two nonbenzenoid NGs (2A,B) containing four embedded azulene units in the polycyclic framework, via on-surface oxidative ring-closure reactions. Interestingly, we observe surface-catalyzed skeletal ring rearrangement reactions in the NGs, which lead to the formation of additional heptagonal rings as well as pentalene and as-indacene units in 2A,B, respectively. 2A,B on Au(111) both exhibit narrow experimental frontier electronic gaps of 0.96 and 0.85 eV, respectively, and Fermi level pinning of their HOMOs together with considerable electron transfer to the substrate. Ab initio calculations estimate moderate open-shell biradical characters for the NGs in the gas phase.

In this work, we demonstrate the first synthesis of vinylene‐linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D‐PPQV1 and 2D‐PPQV2, via the Horner–Wadsworth–Emmons (HWE) reaction of C 2‐symmetric 1,4‐bis(diethylphosphonomethyl)benzene or 4,4′‐bis(diethylphosphonomethyl)biphenyl with C 3‐symmetric 2,3,8,9,14,15‐hexa(4‐formylphenyl)diquinoxalino[2,3‐a:2′,3′‐c]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C−C single bond formation for the synthesis of crystalline 2D CPs. Powder X‐ray diffraction (PXRD) studies and nitrogen adsorption‐desorption measurements demonstrate the formation of proclaimed crystalline, dual‐pore structures with surface areas of up to 440 m2 g−1. More importantly, the optoelectronic properties of the obtained 2D‐PPQV1 (Eg=2.2 eV) and 2D‐PPQV2 (Eg=2.2 eV) are compared with those of cyano‐vinylene‐linked 2D‐CN‐PPQV1 (Eg=2.4 eV) produced by the Knoevenagel reaction and imine‐linked 2D COF analog (2D‐C=N‐PPQV1, Eg=2.3 eV), unambiguously proving the superior conjugation of the vinylene‐linked 2D CPs using the HWE reaction., 2D CPs via the Horner–Wadsworth–Emmons Reaction: A novel methodology for the solvothermal bottom‐up synthesis of 2D vinylene‐linked conjugated polymers (2D CPs) with a nitrogen‐doped skeleton by linking hexaazatrinaphthalene (HATN) units and phenyl/biphenyl units by vinylene linkages is reported.

Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on‐surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well‐controlled ultrahigh‐vacuum conditions. Here we report the on‐surface synthesis of a polymer linked by cumulene‐like bonds on a Au(111) surface via sequential thermally activated dehalogenative C−C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene‐like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X‐ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on‐surface synthesis of cumulene‐containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces., Superficial interactions: On‐surface investigations of tribenzoazulene molecules functionalized with two dibromomethylene groups at the pentagon and heptagon ends reveal, after sequential annealing steps, the unambiguous formation of polymers linked by cumulene‐like bonds via selective C−C coupling induced by the sequential activation of the precursor molecules on a Au(111) surface.

We report on the formation of nitrogen-doped nanographenes containing five- and seven-membered rings by thermally induced cyclodehydrogenation on the Au(111) surface. Using scanning tunneling microscopy and supported by calculations, we investigated the structure of the precursor and targets, as well as of intermediates. Scanning tunneling spectroscopy shows that the electronic properties of the target nanographenes are strongly influenced by the additional formation of non-hexagonal rings.

Nonbenzenoid carbocyclic rings are postulated to serve as important structural elements toward tuning the chemical and electronic properties of extended polycyclic aromatic hydrocarbons (PAHs, or namely nanographenes), necessitating a rational and atomically precise synthetic approach toward their fabrication. Here, using a combined bottom-up in-solution and on-surface synthetic approach, we report the synthesis of nonbenzenoid open-shell nanographenes containing two pairs of embedded pentagonal and heptagonal rings. Extensive characterization of the resultant nanographene in solution shows a low optical gap, and an open-shell singlet ground state with a low singlet-triplet gap. Employing ultra-high-resolution scanning tunneling microscopy and spectroscopy, we conduct atomic-scale structural and electronic studies on a cyclopenta-fused derivative on a Au(111) surface. The resultant five to seven rings embedded nanographene displays an extremely narrow energy gap of 0.27 eV and exhibits a pronounced open-shell biradical character close to 1 (

The electronic and magnetic properties of nanographenes strongly depend on their size, shape and topology. While many nanographenes present a closedshell electronic structure, certain molecular topologies may lead to an open-shell structure. Triangular-shaped nanographenes with zigzag edges, which exist as neutral radicals, are of considerable interest both in fundamental science and for future technologies aimed at harnessing their intrinsic high-spin magnetic ground states for spinbased operations and information storage. Their synthesis, however, is extremely challenging owing to the presence of unpaired electrons, which confers them with enhanced reactivity. We report a combined in-solution and onsurface synthesis of π-extended triangulene, a non-Kekulé nanographene with the structural formula C33H15, consisting of ten benzene rings fused in a triangular fashion. The distinctive topology of the molecule entails the presence of three unpaired electrons that couple to form a spin quartet ground state. The structure of individual molecules adsorbed on an inert gold surface is confirmed through ultrahigh-resolution scanning tunneling microscopy. The electronic properties are studied via scanning tunneling spectroscopy, wherein unambiguous spectroscopic signatures of the spin-split singly occupied molecular orbitals are found. Detailed insight into its properties is obtained through tight-binding, density functional and many-body perturbation theory calculations, with the latter providing evidence that π-extended triangulene retains its open-shell quartet ground state on the surface. Our work provides unprecedented access to open-shell nanographenes with high-spin ground states, potentially useful in carbon-based spintronics.

Covalent organic frameworks (COFs) have aroused immense scientific interest as an exhilarating class of porous materials due to their structure tunability and diverse properties. However, understanding of their response towards laser induced nonlinear optical (NLO) applications is in its infancy and demands prompt attention. Herein, we report three novel regioregular porphyrin based porous COFs, Por‐COF‐HH and its dual metalated congeners (Por‐COF‐ZnCu and Por‐COF‐ZnNi) with excellent NLO properties. Notably, intensity dependent NLO switching behavior was observed for these Por‐COFs, which is highly desirable for optical switching and optical limiting devices. Moreover, the efficient π‐conjugation and charge transfer transition in ZnCu‐Por‐COF enable a high nonlinear absorption coefficient (β=4470 cm/GW) and figure of merit (FOM = σ1/σo, 3565) values compared to other state‐of‐art materials including molecular porphyrins (β=~100‐400 cm/GW), metal‐organic frameworks (MOFs; β=~0.3‐0.5 cm/GW) and graphene (β=900 cm/GW).

Bottom-up synthesis of quasi-one-dimensional graphene nanoribbons (GNRs) with defined structures and controllable properties has attracted great attention for potential applications in electronic a...

Polycyclic aromatic azomethine ylides (PAMYs) are versatile building blocks for the bottom-up construction of unprecedented nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). Here, we demonstrate the 1,3-dipolar cycloaddition between PAMY and 1,4-diphenylbut-2-yne-1,4-dione and the subsequent condensation reaction with hydrazine, which led to unique N-PAHs with a phenyl-substituted pyrrolopyridazine core (PP-1 and PP-2). The molecular structures of pristine PP-1 and tert-butyl-substituted PP-2 were verified by NMR spectroscopy and mass spectrometry. Moreover, the structure of PP-2 was unambiguously elucidated by X-ray single crystal analysis. The optoelectronic properties were investigated by solvent-dependent UV-Vis absorption and fluorescence emission spectroscopy as well as cyclic voltammetry. Additionally, density functional theory (DFT) calculations showed that PP-1 and PP-2 exhibit push-pull behavior. Furthermore, in situ EPR/UV-Vis-NIR spectroelectrochemistry allowed the detailed insight into the spectroscopic properties and spin distribution of radical cation species of PP-2.

Zigzag-edged nanographene with two rows of fused linear acenes, called as n-peri-acene (n-PA), is considered as a potential building unit in the arena of organic electronics. n-PAs with four (peri-tetracene, 4-PA), five (peri-pentacene, 5-PA) or more benzene rings in a row have been predicted to show open-shell character, which would be attractive for the development of unprecedented molecular spintronics. However, solution-based synthesis of open-shell n-PA has thus far not been successful because of the poor chemical stability. Herein we demonstrated the synthesis and characterization of the hitherto unknown 4-PA by a rational strategy in which steric protection of the zigzag edges playing a pivotal role. The obtained 4-PA possesses a singlet biradical character (y0 = 72%) and exhibits remarkable persistent stability with a half-life time (t1/2) of ∼3 h under ambient conditions. UV–vis–NIR and electrochemical measurements reveal a narrow optical/electrochemical energy gap (1.11 eV) for 4-PA. Moreover, t...

Herein, we report on the mechanochemical Scholl reaction of dendritic oligophenylene precursors to produce benchmark nanographenes such as hexa-peri-hexabenzocoronene (HBC), triangular shaped C60 and expanded C222 under solvent-free conditions. The solvent-free approach overcomes the bottleneck of solubility limitation in this well-known and powerful reaction. The mechanochemical approach allows tracking the reaction process by in situ pressure measurements. The quality of produced nanographenes has been confirmed by MALDI-TOF mass spectrometry and UV-Vis absorption spectroscopy. This approach paves the way towards gram scale and environmentally benign synthesis of extended nanographenes and possibly graphene nanoribbons suitable for application in carbon based electronics or energy applications.

Porous organic polymers (POPs) have attracted significant attention towards molecular adsorption in recent years due to their high porosity, diverse functionality and excellent chemical stability. In this work, we present a systematic case study on the formation of thiazolo[5,4-d]thiazole (TzTz) linkages through model compounds and its integration to synthesize a set of three novel, thermo-chemically stable TzTz-linked POPs, namely TzTz-POP-3, TzTz-POP-4, and TzTz-POP-5 with triphenylbenzene, tetraphenylpyrene and tetra(hydroxyphenyl)methane cores, respectively. Interestingly, the integrated TzTz moiety of the represented TzTz-POP-3 renders chemoselective removal of organic dye fluorescein (FL) from a mixture with parafuchsine (FU) in aqueous solution. The TzTz-POP-3 offered excellent chemoselectivity of ≈1:7 (FL:FU), compared to alike porous materials demonstrated for similar applications due to the presence of multiple active anchoring sites coupled with permanent porosity and appropriate pore window.

Nanographenes, namely polycyclic aromatic hydrocarbons (PAHs) with nanoscale dimensions (>1 nm), are atomically precise cutouts from graphene. They represent prime models to enhance the scope of chemical and physical properties of graphene through structural modulation and functionalization. Defined nitrogen doping in nanographenes is particularly attractive due to its potential for increasing the number of π-electrons, with the possibility of introducing localized antiaromatic ring elements. Herein we present azomethine ylide homocoupling as a strategy to afford internally nitrogen-doped, non-planar PAH in solution and planar nanographene on surfaces, with central pyrazine rings. Localized antiaromaticity of the central ring is indicated by optical absorption spectroscopy in conjunction with theoretical calculations. Our strategy opens up methods for chemically tailoring graphene and nanographenes, modified by antiaromatic dopants., Polyaromatic hydrocarbons can be precisely manipulated to yield ever more complex and discrete graphene analogs, such as nanographenes. Here, the authors use azomethine ylide homocoupling to insert an antiaromatic pyrazine ring into the core of a nanographene, and characterize the molecule’s unique electronic character.

On-surface chemistry for atomically precise sp2 macromolecules requires top-down lithographic methods on insulating surfaces in order to pattern the long-range complex architectures needed by the semiconductor industry. Here, we fabricate sp2-carbon nanometer-thin films on insulators and under ultrahigh vacuum (UHV) conditions from photocoupled brominated precursors. We reveal that covalent coupling is initiated by C–Br bond cleavage through photon energies exceeding 4.4 eV, as monitored by laser desorption ionization (LDI) mass spectrometry (MS) and X-ray photoelectron spectroscopy (XPS). Density functional theory (DFT) gives insight into the mechanisms of C–Br scission and C–C coupling processes. Further, unreacted material can be sublimed and the coupled sp2-carbon precursors can be graphitized by e-beam treatment at 500 °C, demonstrating promising applications in photolithography of graphene nanoarchitectures. Our results present UV-induced reactions on insulators for the formation of all sp2-carbon architectures, thereby converging top-down lithography and bottom-up on-surface chemistry into technology., We acknowledge financial support from the European Research Council Advanced Grant DYNamo (ERC-2010-AdG-267374) Spanish Grants (FIS2010-21282-C02-01 and PIB2010US-00652), Grupos Consolidados UPV/EHU del Gobierno Vasco (IT578-13), Ikerbasque and the European Commission projects CRONOS (Grant 280879-2 CRONOS CP-FP7). C.-A.P. and K.D. were funded through the ERC Advanced Grant MolArt (no. 247299). D.J.M. acknowledges funding through the Spanish “Juan de la Cireva” program (JCI-2010-08156). J.L.C acknowledges funding through the Mexican CONACyT program.

We report the first synthesis of a persulfurated polycyclic aromatic hydrocarbon (PAH) as a next-generation “sulflower.” In this novel PAH, disulfide units establish an all-sulfur periphery around a coronene core. The structure, electronic properties, and redox behavior were investigated by microscopic, spectroscopic and electrochemical methods and supported by density functional theory. The sulfur-rich character of persulfurated coronene renders it a promising cathode material for lithium–sulfur batteries, displaying a high capacity of 520 mAh g–1 after 120 cycles at 0.6 C with a high-capacity retention of 90%.

Graphene nanoribbons (GNRs), quasi-one-dimensional graphene strips, have shown great potential for nanoscale electronics, optoelectronics, and photonics. Atomically precise GNRs can be "bottom-up" synthesized by surface-assisted assembly of molecular building blocks under ultra-high-vacuum conditions. However, large-scale and efficient synthesis of such GNRs at low cost remains a significant challenge. Here we report an efficient "bottom-up" chemical vapor deposition (CVD) process for inexpensive and high-throughput growth of structurally defined GNRs with varying structures under ambient-pressure conditions. The high quality of our CVD-grown GNRs is validated by a combination of different spectroscopic and microscopic characterizations. Facile, large-area transfer of GNRs onto insulating substrates and subsequent device fabrication demonstrate their promising potential as semiconducting materials, exhibiting high current on/off ratios up to 6000 in field-effect transistor devices. This value is 3 orders of magnitude higher than values reported so far for other thin-film transistors of structurally defined GNRs. Notably, on-surface mass spectrometry analyses of polymer precursors provide unprecedented evidence for the chemical structures of the resulting GNRs, especially the heteroatom doping and heterojunctions. These results pave the way toward the scalable and controllable growth of GNRs for future applications.

A novel class of dibenzo-fused 1,9-diaza-9a-boraphenalenes featuring zigzag edges with a nitrogen-boron-nitrogen bonding pattern named NBN-dibenzophenalenes (NBN-DBPs) has been synthesized. Alternating nitrogen and boron atoms impart high chemical stability to these zigzag-edged polycyclic aromatic hydrocarbons (PAHs), and this motif even allows for postsynthetic modifications, as demonstrated here through electrophilic bromination and subsequent palladium-catalyzed cross-coupling reactions. Upon oxidation, as a typical example, NBN-DBP 5a was nearly quantitatively converted to σ-dimer 5a-2 through an open-shell intermediate, as indicated by UV-vis-NIR absorption spectroscopy and electron paramagnetic resonance spectroscopy corroborated by spectroscopic calculations, as well as 2D NMR spectra analyses. In situ spectroelectrochemistry was used to confirm the formation process of the dimer radical cation 5a-2(•+). Finally, the developed new synthetic strategy could also be applied to obtain π-extended NBN-dibenzoheptazethrene (NBN-DBHZ), representing an efficient pathway toward NBN-doped zigzag-edged graphene nanoribbons.

Based on polycyclic aromatic azomethine ylides (PAMYs), a metal-free “cycloaddition-planarization-sequence” is proposed, providing a unique entry to extended nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). This method is highly versatile, as the structure of unprecedented N-PAHs can be tailored by the dipolarophile in the crucial 1,3-cycloaddition-reaction. Linear, as well as five- and six-membered cyclic dipolarophiles are successfully used. The geometric and optoelectronic nature of N-PAHs are investigated by UV-vis absorption and single crystal structure analysis. Remarkably, the newly synthesized N-PAHs demonstrate varying absorption profiles, covering the whole visible light range with rich photophysical properties, for example, fluorescent quantum yields up to 54%.

In this communication, we report that dipotassium aryl bis(trifluoroborate)s make stable and easy-to-purify yet reactive monomers under Suzuki polycondensation reactions. A bis(trifluoroborate) of 2-alkylbenzotriazole was prepared successfully and copolymerized with dibromobenzothiadiazole in the presence of a Pd catalyst and LiOH, yielding high molecular weight conjugated polymers. This polymer (P1) composed of all electron-accepting units shows excellent electron-transport properties (μ(e) = 0.02 cm(2) V(-1) s(-1)), which proves the value of the aryl bis(trifluoroborate) monomers and suggests that many other types of semiconducting polymers that could not be accessed previously can be synthesized using this approach.

Based on modern pyrene chemistry, a new route toward the synthesis of the peri-pentacene framework was developed. Firstly, the tetraketo form as stable precursor was targeted, because the fully aromatic peri-pentacene is predicted to suffer from high instability and reactivity. Therefore, a recently developed 4,5,9,10-tetrafunctionalization of pyrene was utilized to build up a planar and a dragonfly-shaped derivative in five steps, which only differ in the two outer bonds between the peripheral benzene rings. The planar tetraketone could only be dissolved in strong acids upon protonation, which limited the use of analytical methods. In contrast, the dragonfly-shaped form showed excellent organosolubility. In-depth investigation by NMR spectroscopy revealed co-existence of atropo-isomers in solution. The optical and electronic properties were analyzed by UV/Vis spectroscopy and cyclic voltammetry. To approach aromatic conjugation, stepwise reduction in solution by using tetrabutylammonium borohydride was carried out. Reduced species were studied by ESR and UV/Vis spectroscopy, as well as by MALDI-TOF MS, confirming the formation of the radical anion.

Diindeno-fused bischrysene, a new diindeno-based polycyclic hydrocarbon (PH), was synthesized and characterized. It was elucidated in detailed experimental and theoretical studies that this cyclopenta-fused PH possesses an open-shell singlet biradical structure in the ground state and exhibits high stability under ambient conditions (t1/2=39 days). The crystal structure unambiguously shows a novel saddle-shaped π-conjugated carbon skeleton due to the steric hindrance of the central cove-edged bischrysene unit. UV/Vis spectral measurements revealed that the title molecule has a very narrow optical energy gap of 0.92 eV, which is consistent with the electrochemical analysis and further supported by density functional theory (DFT) calculations.

Cyano-substituted polyphenylene vinylenes (PPVs) have been the focus of research for several decades owing to their interesting optoelectronic properties and potential applications in organic electronics. With the advent of organic two-dimensional (2D) crystals, the question arose as to how the chemical and optoelectronic advantages of PPVs evolve in 2D compared with their linear counterparts. In this work, we present the efficient synthesis of two novel 2D fully sp2 -carbon-linked crystalline PPVs and investigate the essentiality of inorganic bases for their catalytic formation. Notably, among all bases screened, cesium carbonate (Cs2 CO3 ) plays a crucial role and enables reversibility in the first step with subsequent structure locking by formation of a C=C double bond to maintain crystallinity, which is supported by density functional theory (DFT) calculations. A quantifiable energy diagram of a "quasi-reversible reaction" is proposed, which allows the identification of further suitable C-C bond formation reactions for 2D polymerizations. Moreover, the narrowing of the HOMO-LUMO gap is delineated by expanding the conjugation into two dimensions. To enable environmentally benign processing, the post-modification of 2D PPVs is further performed, which renders stable dispersions in the aqueous phase.

Total synthetic approaches of fullerenes are the holy grail for organic chemistry. So far, the main attempts have focused on the synthesis of the buckminsterfullerene C60. In contrast, access to subunits of the homologue C70 remains challenging. Here, we demonstrate an efficient bottom-up strategy toward a novel bowl-shaped polycyclic aromatic hydrocarbons (PAH) C34 with two pentagons. This PAH represents a subunit for C70 and of other higher fullerenes. The bowl-shaped structure was unambiguously determined by X-ray crystallography. A bowl-to-bowl inversion for a C70 fragment in solution was investigated by dynamic NMR analysis, showing a bowl-to-bowl inversion energy (ΔG(⧧)) of 16.7 kcal mol(-1), which is further corroborated by DFT calculations.

[Image: see text] On-surface synthesis provides an effective approach toward the formation of graphene nanostructures that are difficult to achieve via traditional solution chemistry. Here, we report on the design and synthesis of a nonplanar porous nanographene with 78 sp(2) carbon atoms, namely C78. Through a highly selective oxidative cyclodehydrogenation of 2,3,6,7,10,11-hexa(naphthalen-1-yl)triphenylene (2), propeller nanographene precursor 1 was synthesized in solution. Interestingly, although 1 could not be cyclized further in solution, porous nanographene C78 was successfully achieved from 1 by on-surface assisted cyclodehydrogenation on Au(111). The structure and electronic properties of C78 have been investigated by means of scanning tunneling microscopy, noncontact atomic force microscopy, and scanning tunneling spectroscopy, complemented by computational investigations. Our results provide perspectives for the on-surface synthesis of porous graphene nanostructures, offering a promising strategy for the engineering of graphene materials with tailor-made properties.