Cyclodehydrogenation Reaction Research Articles

Biaryl Anion Radical Formation by Potassium Metal Reduction of Aryl Isocyanates and Triaryl Isocyanurates.

The potassium metal reduction of aryl isocyanates (aryl = phenyl, p-tolyl, 3,5-dimethylphenyl, 4-biphenylyl, and 1-naphthyl) in THF with 18-crown-6 or in HMPA results in the formation of the corresponding triaryl isocyanurate anion radicals. Continued exposure to potassium results in loss of the isocyanurate anion radical and the eventual formation of the respective biaryl anion radical. The 1,1'-binaphthyl anion radical is found to undergo a cyclodehydrogenation reaction, which leads to formation of the perylene anion radical. When authentic triaryl isocyanurates are reduced with metal, the heterocyclic ring undergoes fragmentation with elimination of carbon monoxide to produce a triarylbiuret dianion. This ring opening reaction is initiated by the two-electron reduction of the neutral isocyanurate species. The biaryl anion radical is formed when the biuret dianion is reduced further with metal. A possible mechanism for biaryl formation involves a heterolytic cleavage of an aryl C-N bond and release of an aryl radical once the triarylbiuret dianion is further reduced. A subsequent intermolecular reaction between two aryl radicals forms the corresponding biaryl, which can then be reduced to the anion radical. Notably, when a mixture of two different triaryl isocyanurate compounds is reduced in solution, the corresponding mixed biaryl anion radical is generated.

A Cascade Reaction Triggered by H‐H Steric Hindrance: Dimeric Covalent Organic Frameworks on Au(111) and Dimeric Nanoribbons on Ag(111)

Comprehensive SummaryIn on‐surface synthesis, dimers are typically utilized to explore reaction mechanisms or as intermediates in the formation of final products. However, constructing the innovative nanostructures with dimers as building blocks remains challenging. Here, using non‐planar 2,2′,7,7′‐tetrabromo‐9,9′‐biflurenyliden molecules, we have successfully synthesized dimeric covalent organic frameworks (COFs) on the Au(111) surface through a temperature‐controlled cascade reaction. Notably, the H‐H steric hindrance within precursors caused by double bonds leads to selective stepwise debromination during the thermal annealing, which promotes the dimerization through intermolecular Ullmann coupling and cyclodehydrogenation reaction to form COFs primarily constituted by dimer building blocks. Combining scanning tunneling microscopy/spectroscopy and density functional theory calculations, we have precisely confirmed the structural evolution and reaction mechanism. Furthermore, by introducing Ag adatoms to form C−Ag−C intermediates, we have successfully regulated the reaction path and synthesized one‐dimensional nanoribbons with dimers as building blocks. This work not only validates the strategy of synthesizing dimeric nanostructures on different surfaces through cascade reactions induced by precursor design, but also enriches the research field of surface synthesis of COFs and nanoribbons.

An AIEE-active Triphenylethylene Derivative with Photoresponsive Character for Latent Fingerprints Detection via a Simple Soaking Method.

Latent fingerprints (LFPs) is one of the most important physical evidence in the criminal scene, playing an important role in forensic investigations. Therefore, developing highly sensitive and convenient materials for the visualization of LFPs is of great significance. We designed and synthesized an organic fluorescent molecule TP-PH with aggregation-induced enhanced emission (AIEE) activity. By simply soaking, blue fluorescent images with high contrast and resolution are readily developed on various surfaces including tinfoil, steel, glass and plastic. Remarkably, LFPs can be visualized within 5min including the first-, second- and tertiary-level details. In addition, TP-PH exhibits interesting photoactivated fluorescence enhancement properties. Under irradiation of 365nm UV light with a power density of 382 mW/cm2, the fluorescence quantum yield displays approximately 21.5-fold enhancement. Mechanism studies reveals that the photoactivated fluorescence is attributed to the irreversible cyclodehydrogenation reactions under UV irradiation. This work provides a guideline for the design of multifunctional AIEE fluorescent materials.

Phenanthrothiophene-Triazine Star-Shaped Discotic Liquid Crystals: Synthesis, Self-Assembly, and Stimuli-Responsive Fluorescence Properties.

Lipophilic biphenylthiophene- and phenanthrothiophene-triazine compounds, BPTTn and CPTTn, respectively, were prepared by a tandem procedure involving successive Suzuki-Miyaura coupling and Scholl cyclodehydrogenation reactions. These compounds display photoluminescence in solution and in thin film state, solvatochromism with increasing solvent's polarity, as well as acidochromism and metal ion recognition stimuli-responsive fluorescence. Protonation of BPTT10 and CPTT10 by trifluoroacetic acid results in fluorescence quenching, which is reversibly restored once treated with triethylamine (ON-OFF switch). DFT computational studies show that intramolecular charge transfer (ICT) phenomena occurs for both molecules, and reveal that protonation enhances the electron-withdrawing ability of the triazine core and reduces the band gap. This acidochromic behavior was applied to a prototype fluorescent anti-counterfeiting device. They also specifically recognize Fe3+ through coordination, and the recognition mechanism is closely related to the photoinduced electron transfer between Fe3+ and BPTT10/CPTT10. CPTTn self-assemble into columnar rectangular (Colrec) mesophase, which can be modulated by oleic acid via the formation of a hydrogen-bonded supramolecular liquid crystal hexagonal Colhex mesophase. Finally, CPTTn also form organic gels in alkanes at low critical gel concentration (3.0 mg/mL). Therefore, these star-shaped triazine molecules possess many interesting features and thus hold great promises for information processing, liquid crystal semiconductors and organogelators.

Highly Regioselective Cyclodehydrogenation of Diphenylporphyrin on Metal Surfaces.

Exploring the effect of porphin tautomerism on the regioselectivity of its derivatives is a big challenge, which is significant for the development and application of porphyrin drugs. In this work, we demonstrate the regioselectivity of 2H-diphenylporphyrin (H2-DPP) in the planarization reaction on Au(111) and Ag(111) substrates. H2-DPP monomer forms two configurations (anti- and syn-) via a dehydrogenation coupling, between which the yield of the anti-configuration exceeds 90%. Using high-resolution scanning tunneling microscopy, we visualize the reaction processes from the H2-DPP monomer to the final two planar products. Combined with DFT calculations of the potential reaction pathway and comparative experiments on Au(111) and Ag(111) substrates. Using M-DPP (M = Cu and Fe), we confirm that the regioselectivity of H2-DPP is derived from the reaction energy barrier during the cyclodehydrogenation reaction of different tautomers. This work reveals the regioselectivity mechanism of H2-DPP on the atomic scale, which holds great significance for understanding the chemical conversion process of organic macrocyclic molecules.

On-Surface Synthesis of Pentagon-Incorporated Graphene-Like Nanoribbons with Multiple Precursors

Graphene nanoribbons (GNRs) and their derivatives are receiving increasing attention as a result of their unique electronic and magnetic properties, and many novel derivative structures have been fabricated. The carbon pentagon plays a crucial role in determining both geometric structures and electronic properties of carbon-based materials. Here, we demonstrate that carbon-pentagon-incorporated graphene-like nanoribbons (GLNRs), which are an important class of GNR derivatives, are successfully fabricated via the Ullmann coupling and aromatic cyclodehydrogenation reaction on the surface by a suitable choice of multiple tailored molecular precursors. Our approach provides a basis for the impact of adatoms in the reaction and proves the steering function of the aryl-metal interaction in procedures of self-assembly and organometallic state. In addition, this study paves the way for on-surface synthesis of GNRs and their derivatives as well as the fine tuning of electronic properties of carbon nanoarchitectures by manipulating the edge structures and embedding carbon pentagon heterojunctions.

Remote-Triggered Domino-like Cyclodehydrogenation in Second-Layer Topological Graphene Nanoribbons

Cyclodehydrogenation reactions in the on-surface synthesis of graphene nanoribbons (GNRs) usually involve a series of Csp2-Csp2 and/or Csp2-Csp3 couplings and just happen on uncovered metal or metal oxide surfaces. It is still a big challenge to extend the growth of second-layer GNRs in the absence of necessary catalytic sites. Here, we demonstrate the direct growth of topologically nontrivial GNRs via multistep Csp2-Csp2 and Csp2-Csp3 couplings in the second layer by annealing designed bowtie-shaped precursor molecules over one monolayer on the Au(111) surface. After annealing at 700 K, most of the polymerized chains that appear in the second layer covalently link to the first-layer GNRs that have partially undergone graphitization. Following annealing at 780 K, the second-layer GNRs are formed and linked to the first-layer GNRs. Benefiting from the minimized local steric hindrance of the precursors, we suggest that the second-layer GNRs undergo domino-like cyclodehydrogenation reactions that are remotely triggered at the link. We confirm the quasi-freestanding behaviors in the second-layer GNRs by measuring the quasiparticle energy gap of topological bands and the tunable Kondo resonance from topological end spins using scanning tunneling microscopy/spectroscopy combined with first-principles calculations. Our findings pave the avenue to diverse multilayer graphene nanostructures with designer quantum spins and topological states for quantum information science.

Lithium-Mediated Mechanochemical Cyclodehydrogenation

Cyclodehydrogenation is an essential synthetic method for the preparation of polycyclic aromatic hydrocarbons, polycyclic heteroaromatic compounds, and nanographenes. Among the many examples, anionic cyclodehydrogenation using potassium(0) has attracted synthetic chemists because of its irreplaceable reactivity and utility in obtaining rylene structures from binaphthyl derivatives. However, existing methods are difficult to use in terms of practicality, pyrophoricity, and lack of scalability and applicability. Herein, we report the development of a lithium(0)-mediated mechanochemical anionic cyclodehydrogenation reaction for the first time. This reaction could be easily performed using a conventional and easy-to-handle lithium(0) wire at room temperature, even under air, and the reaction of 1,1'-binaphthyl is complete within 30 min to afford perylene in 94% yield. Using this novel and user-friendly protocol, we investigated substrate scope, reaction mechanism, and gram-scale synthesis. As a result, remarkable applicability and practicality over previous methods, as well as limitations, were comprehensively studied by computational studies and nuclear magnetic resonance analysis. Furthermore, we demonstrated two-, three-, and five-fold cyclodehydrogenations for the synthesis of novel nanographenes. In particular, quinterrylene ([5]rylene or pentarylene), the longest nonsubstituted molecular rylene, was synthesized for the first time.

Collective Quantum Magnetism in Nitrogen-Doped Nanographenes.

The emergence of quantum magnetism in nanographenes provides ample opportunities to fabricate purely organic devices for spintronics and quantum information. Although heteroatom doping is a viable way to engineer the electronic properties of nanographenes, the synthesis of doped nanographenes with collective quantum magnetism remains elusive. Here, a set of nitrogen-doped nanographenes (N-NGs) with atomic precision are fabricated on Au(111) through a combination of imidazole [2+2+2]-cyclotrimerization and cyclodehydrogenation reactions. High-resolution scanning probe microscopy measurements reveal the presence of collective quantum magnetism for nanographenes with three radicals, with spectroscopic features which cannot be captured by mean-field density functional theory calculations but can be well reproduced by Heisenberg spin model calculations. In addition, the mechanism of magnetic exchange interaction of N-NGs has been revealed and compared with their counterparts with pure hydrocarbons. Our findings demonstrate the bottom-up synthesis of atomically precise N-NGs which can be utilized to fabricate low-dimensional extended graphene nanostructures for realizing ordered quantum phases.

Pyrene-Fused Poly-Aromatic Regioisomers: Synthesis, Columnar Mesomorphism, and Optical Properties.

π-Extended pyrene compounds possess remarkable luminescent and semiconducting properties and are being intensively investigated as electroluminescent materials for potential uses in organic light-emitting diodes, transistors, and solar cells. Here, the synthesis of two sets of pyrene-containing π-conjugated polyaromatic regioisomers, namely 2,3,10,11,14,15,20,21-octaalkyloxypentabenzo[a,c,m,o,rst]pentaphene (BBPn) and 2,3,6,7,13,14,17,18-octaalkyloxydibenzo[j,tuv]phenanthro [9,10-b]picene (DBPn), is reported. They were obtained using the Suzuki-Miyaura cross-coupling in tandem with Scholl oxidative cyclodehydrogenation reactions from the easily accessible precursors 1,8- and 1,6-dibromopyrene, respectively. Both sets of compounds, equipped with eight peripheral aliphatic chains, self-assemble into a single hexagonal columnar mesophase, with one short-chain BBPn homolog also exhibiting another columnar mesophase at a lower temperature, with a rectangular symmetry; BBPn isomers also possess wider mesophase ranges and higher mesophases' stability than their DBPn homologs. These polycyclic aromatic hydrocarbons all show a strong tendency of face-on orientation on the substrate and could be controlled to edge-on alignment through mechanical shearing of interest for their implementation in photoelectronic devices. In addition, both series BBPn and DBPn display green-yellow luminescence, with high fluorescence quantum yields, around 30%. In particular, BBPn exhibit a blue shift phenomenon in both absorption and emission with respect to their DBPn isomers. DFT results were in good agreement with the optical properties and with the stability ranges of the mesophases by confirming the higher divergence from the flatness of DBPn compared with BBPn. Based on these interesting properties, these isomers could be potentially applied not only in the field of fluorescent dyes but also in the field of organic photoelectric semiconductor materials as electron transport materials.

On-Surface Synthesis of Nanographenes and Graphene Nanoribbons on Titanium Dioxide.

The formation of two types of nanographenes from custom designed and synthesized molecular precursors has been achieved through thermally induced intramolecular cyclodehydrogenation reactions on the semiconducting TiO2(110)-(1×1) surface, confirmed by the combination of high-resolution scanning tunneling microscopy (STM) and spectroscopy (STS) measurements, and corroborated by theoretical modeling. The application of this protocol on differently shaped molecular precursors demonstrates the ability to induce a highly efficient planarization reaction both within strained pentahelicenes as well as between vicinal phenyl rings. Additionally, by the combination of successive Ullmann-type polymerization and cyclodehydrogenation reactions, the archetypic 7-armchair graphene nanoribbons (7-AGNRs) have also been fabricated on the titanium dioxide surface from the standard 10,10'-dibromo-9,9'-bianthryl (DBBA) molecular precursors. These examples of the effective cyclodehydrogenative planarization processes provide perspectives for the rational design and synthesis of molecular nanostructures on semiconductors.

The Role of Metal Adatoms in a Surface‐Assisted Cyclodehydrogenation Reaction on a Gold Surface

AbstractDehydrogenation reactions are key steps in many metal‐catalyzed chemical processes and in the on‐surface synthesis of atomically precise nanomaterials. The principal role of the metal substrate in these reactions is undisputed, but the role of metal adatoms remains, to a large extent, unanswered, particularly on gold substrates. Here, we discuss their importance by studying the surface‐assisted cyclodehydrogenation on Au(111) as an ideal model case. We choose a polymer theoretically predicted to give one of two cyclization products depending on the presence or absence of gold adatoms. Scanning probe microscopy experiments observe only the product associated with adatoms. We challenge the prevalent understanding of surface‐assisted cyclodehydrogenation, unveiling the catalytic role of adatoms and their effect on regioselectivity. The study adds new perspectives to the understanding of metal catalysis and the design of on‐surface synthesis protocols for novel carbon nanomaterials.

The Role of Metal Adatoms in a Surface-Assisted Cyclodehydrogenation Reaction on a Gold Surface.

Dehydrogenation reactions are key steps in many metal-catalyzed chemical processes and in the on-surface synthesis of atomically precise nanomaterials. The principal role of the metal substrate in these reactions is undisputed, but the role of metal adatoms remains, to a large extent, unanswered, particularly on gold substrates. Here, we discuss their importance by studying the surface-assisted cyclodehydrogenation on Au(111) as an ideal model case. We choose a polymer theoretically predicted to give one of two cyclization products depending on the presence or absence of gold adatoms. Scanning probe microscopy experiments observe only the product associated with adatoms. We challenge the prevalent understanding of surface-assisted cyclodehydrogenation, unveiling the catalytic role of adatoms and their effect on regioselectivity. The study adds new perspectives to the understanding of metal catalysis and the design of on-surface synthesis protocols for novel carbon nanomaterials.

Momentum space imaging of σ orbitals for chemical analysis.

Tracing the modifications of molecules in surface chemical reactions benefits from the possibility to image their orbitals. While delocalized frontier orbitals with π character are imaged routinely with photoemission orbital tomography, they are not always sensitive to local chemical modifications, particularly the making and breaking of bonds at the molecular periphery. For such bonds, σ orbitals would be far more revealing. Here, we show that these orbitals can indeed be imaged in a remarkably broad energy range and that the plane wave approximation, an important ingredient of photoemission orbital tomography, is also well fulfilled for these orbitals. This makes photoemission orbital tomography a unique tool for the detailed analysis of surface chemical reactions. We demonstrate this by identifying the reaction product of a dehalogenation and cyclodehydrogenation reaction.

Inside Cover: Synthesis and Characterization of peri‐Heptacene on a Metallic Surface (Angew. Chem. Int. Ed. 23/2022)

The precursor 4,5,9,10-tetrakis(3-methylnaphthalen-2-yl)pyrene is synthesized in solution, sublimed on an Au(111) substrate under ultra-high vacuum conditions and converted into the peri-heptacene molecule by thermal activation via surface-assisted oxidative ring-closure and cyclodehydrogenation reactions. Details of this research can be found in the Communcation by José I. Urgel, Pavel Jelínek, Xinliang Feng, David Écija et al. (DOI: 10.1002/anie.202114983).

Synthesis of Distorted Nitrogen-Doped Nanographenes by Partially Oxidative Cyclodehydrogenation Reaction.

A series of partially fused N-doped nanographenes (2-4) are synthesized via the oxidative cyclodehydrogenation of oligoaryl-substituted dibenzo[e,l]pyrene (1), and five, six, and seven new C-C bonds are formed, respectively, implying stepwise C-C bond fusion and extended π-conjugation. Single-crystal X-ray diffraction analysis of compound 4 a revealed that the presence of sterically demanding groups hindered the formation of planar and fully fused nanographene in the oxidative cyclodehydrogenation reaction step. Optical study of compounds 2 to 4 showed that extended π-conjugation leads to a regular stepwise bathochromic shift in the absorption and emission spectra. Furthermore, the HOMO-LUMO gaps of these compounds exhibit a decrease as C-C bond formation proceeds. Thus, the optoelectronic properties of nanographenes are highly dependent on the formation of new C-C bonds in the molecular skeleton.

Ditriphenylenothiophene butterfly-shape liquid crystals. The influence of polyarene core topology on self-organization, fluorescence and photoconductivity

Two series of regio-isomeric mesomorphous, luminescent and conductive compounds, based on a ditriphenylenothiophene core (α/β-DTPT), were successfully synthesized by the Suzuki–Miyaura cross-coupling/Scholl cyclo-dehydrogenation reactions tandem.

Butterfly-like Shape Liquid Crystals Based Fused-Thiophene as Unidimensional Ambipolar Organic Semiconductors with High Mobility.

Mesomorphous butterfly-like shape molecules based on benzodithiophene, benzodithiophene-4,8-dione and cyclopentadithiophen-4-one core moieties were efficiently synthesized by the Suzuki-Miyaura coupling and Scholl oxidative cyclo-dehydrogenation reactions' tandem. Most of the butterfly molecules spontaneously self-organize into columnar hexagonal mesophase. The electron-deficient systems possess strong solvent-gelling ability but are not luminescent, whereas the electron-rich terms do not form gels but strongly emit light between 400 and 600 nm. The charge carrier mobility was also measured by time-of-flight transient photocurrent technique in the mesophases for some of the compounds. They display hole-transport performances with positive charge mobility in the 10-3 cm-2 V-1 s-1 range, consistent with the high degree of ordering and stability of the columnar superstructures. In particular, the mesogen with a benzodithiophen-4,8-dione core shows ambipolar charge carrier transport with both high electron (μe =6.6×10-3 cm-2 V-1 s-1 ) and hole (μh =4.5×10-3 cm-2 V-1 s-1 ) mobility values.

Tunable Interface of Ruthenium Porphyrins and Silver

The adsorption and monolayer self-assembly of functional metal–organic blocks on solid surfaces are critical for the physicochemical properties of these low-dimensional materials. Although modern microscopy tools are very sensitive to the lateral arrangement of such blocks, they are still unable to offer directly the complete structural analysis especially for nonplanar molecules containing different atoms. Here, we apply a combinatorial approach for the characterization of such interfaces, which enables unexpected insights. An archetypal metalloporphyrin on a catalytically active surface as a function of its molecular coverage and substituent arrangement is characterized by low-energy electron diffraction, scanning probe microscopy, X-ray photoelectron spectroscopy, normal-incidence X-ray standing waves, and density functional theory. We look into Ru tetraphenyl porphyrin (Ru-TPP) on Ag(111), which is also converted into its planarized derivates via surface-assisted cyclodehydrogenation reactions. Depending on the arrangement of the phenyl substituents, the Ru atoms have distinct electronic structures and the porphyrin macrocycles adapt differently to the surface: saddle shape (pristine Ru-TPP) or bowl shape (planarized Ru-TPP derivates). In all cases, the Ru atom resides close to the surface (2.59/2.45 Å), preferably located at hollow sites and in the interface between the plane of the porphyrin macrocycle and the Ag surface. For the more flexible pristine Ru-TPP, we identify an additional self-assembled structure, allowing the molecular density of the self-assembled monolayer to be tuned within ∼20%. This precise analysis is central to harnessing the potential of metalloporphyrin/metal interfaces in functional systems.

On-surface cyclodehydrogenation reaction pathway determined by selective molecular deuterations.

Understanding the reaction mechanisms of dehydrogenative Caryl–Caryl coupling is the key to directed formation of π-extended polycyclic aromatic hydrocarbons. Here we utilize isotopic labeling to identify the exact pathway of cyclodehydrogenation reaction in the on-surface synthesis of model atomically precise graphene nanoribbons (GNRs). Using selectively deuterated molecular precursors, we grow seven-atom-wide armchair GNRs on a Au(111) surface that display a specific hydrogen/deuterium (H/D) pattern with characteristic Raman modes. A distinct hydrogen shift across the fjord of Caryl–Caryl coupling is revealed by monitoring the ratios of gas-phase by-products of H2, HD, and D2 with in situ mass spectrometry. The identified reaction pathway consists of a conrotatory electrocyclization and a distinct [1,9]-sigmatropic D shift followed by H/D eliminations, which is further substantiated by nudged elastic band simulations. Our results not only clarify the cyclodehydrogenation process in GNR synthesis but also present a rational strategy for designing on-surface reactions towards nanographene structures with precise hydrogen/deuterium isotope labeling patterns.