Observation of fractional edge excitations in nanographene spin chains.

Fractionalization is a phenomenon in which strong interactions in a quantum system drive the emergence of excitations with quantum numbers that are absent in the building blocks. Outstanding examples are excitations with charge e/3 in the fractional quantum Hall effect1,2, solitons in one-dimensional conducting polymers3,4 and Majorana states in topological superconductors5. Fractionalization is also predicted to manifest itself in low-dimensional quantum magnets, such as one-dimensional antiferromagnetic S = 1 chains. The fundamental features of this system are gapped excitations in the bulk6 and, remarkably, S = 1/2 edge states at the chain termini7-9, leading to a four-fold degenerate ground state that reflects the underlying symmetry-protected topological order10,11. Here, we use on-surface synthesis12 to fabricate one-dimensional spin chains that contain the S = 1 polycyclic aromatic hydrocarbon triangulene as the building block. Using scanning tunnelling microscopy and spectroscopy at 4.5 K, we probe length-dependent magnetic excitations at the atomic scale in both open-ended and cyclic spin chains, and directly observe gapped spin excitations and fractional edge states therein. Exact diagonalization calculations provide conclusive evidence that the spin chains are described by the S = 1 bilinear-biquadratic Hamiltonian in the Haldane symmetry-protected topological phase. Our results open a bottom-up approach to study strongly correlated phases in purely organic materials, with the potential for the realization of measurement-based quantum computation13.

Structural Expansion of Cyclohepta[def]fluorene towards Azulene-Embedded Non-Benzenoid Nanographenes.

Non-benzenoid non-alternant nanographenes (NGs) have attracted increasing attention on account of their distinct electronic and structural features in comparison to their isomeric benzenoid counterparts. In this work, we present a series of unprecedented azulene-embedded NGs on Au(111) during the attempted synthesis of cyclohepta[def]fluorene-based high-spin non-Kekulé structure. Comprehensive scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM) evidence the structures and conformations of these unexpected products. The dynamics of the precursor bearing 9-(2,6-dimethylphenyl)anthracene and dihydro-dibenzo-cyclohepta[def]fluorene units and its reaction products on the surface are analyzed by density functional theory (DFT) and molecular dynamics (MD) simulations. Our study sheds light on the fundamental understanding of precursor design for the fabrication of π-extended non-benzenoid NGs on a metal surface.

Modular Synthesis of Structurally Diverse Azulene-Embedded Polycyclic Aromatic Hydrocarbons by Knoevenagel-Type Condensation.

The research interest in azulene-embedded polycyclic aromatic hydrocarbons (PAHs) has significantly increased recently, but the lack of efficient synthetic strategies impedes the investigation of their structure-property relationships and further opto-electronic applications. Here we report a modular synthetic strategy towards diverse azulene-embedded PAHs by a tandem Suzuki coupling and base-promoted Knoevenagel-type condensation with good yields and great structural versatility, including non-alternant thiophene-rich PAHs, butterfly- or Z-shaped PAHs bearing two azulene units, and the first example of a two-azulene-embedded double [5]helicene. The structural topology, aromaticity and photophysical properties were investigated by NMR, X-ray crystallography analysis and UV/Vis absorption spectroscopy assisted by DFT calculations. This strategy provides a new platform for rapidly synthesizing unexplored non-alternant PAHs or even graphene nanoribbons with multiple azulene units.

Copper-Catalyzed Boroaminomethylation of Olefins to γ-Boryl Amines with CO as C1 Source.

Boroaminomethylation of olefins is an efficient process to convert hydrocarbons directly into boron-, nitrogen-containing molecules. Such chemicals are a good handle for obtaining more complexed amine derivatives through the various transformations of organoboron. However, using simple and easily available CO as the C1 feedstock to achieve boroaminomethylation is still elusive. Here we report a copper-catalyzed boroaminomethylation of olefins with CO as the C1 source via the mechanism of a carbene insertion into the N-H bond. This method affords valuable γ-boryl amines from four inexpensive readily chemicals. The wide synthetic transformations of the γ-boryl amines demonstrates their utility. Notably, 13 C labeling studies revealed that the -CH2 -building block was derived from one molecule of CO.

Benzo-Extended Cyclohepta[def]fluorene Derivatives with Very Low-Lying Triplet States.

Open-shell non-alternant polycyclic hydrocarbons (PHs) are attracting increasing attention due to their promising applications in organic spintronics and quantum computing. Herein we report the synthesis of three cyclohepta[def]fluorene-based diradicaloids (1-3), by fusion of benzo rings on its periphery for the thermodynamic stabilization, as evidenced by multiple characterization techniques. Remarkably, all of them display a very narrow optical energy gap (Eg opt =0.52-0.69 eV) and persistent stability under ambient conditions (t1/2 =11.7-33.3 h). More importantly, this new type of diradicaloids possess a low-lying triplet state with an extremely small singlet-triplet energy gap, as low as 0.002 kcal mol-1 , with a clear dependence on the molecular size. This family of compounds thus offers a new route to create non-alternant open-shell PHs with high-spin ground states, and opens up novel possibilities and insights into understanding the structure-property relationships.

First-Row Transition-Metal-Catalyzed Carbonylative Transformations of Carbon Electrophiles.

The main contributions in the field of first-row transition-metal-catalyzed (base-metal-catalyzed) carbonylative transformations have been summarized and discussed. The contents have been divided according to the electrophiles applied, followed by the different types of nucleophiles. Their reaction mechanisms and applications have been emphatically discussed.

Ligand-Controlled Copper-Catalyzed Regiodivergent Carbonylative Synthesis of α-Amino Ketones and α-Boryl Amides from Imines and Alkyl Iodides.

Regioselective transformation is among the long-standing challenges in organic synthesis. In this communication, a copper-catalyzed selectivity controlled regiodivergent borocarbonylation of imines with alkyl iodides has been developed. Various α-amino ketones and α-boryl amides were produced in moderate to good yields from the same substrates. The choice of the ligand is key for the regioselectivity control: α-amino ketones were produced selectively in good yields with (p-CF3 C6 H4 )3 P as the ligand, whereas the corresponding α-boryl amides were obtained with high regioselectivities when using Me IMes as the ligand.

Copper-Catalyzed 1,2-Trifluoromethylation Carbonylation of Unactivated Alkenes: Efficient Access to ß-Trifluoromethylated Aliphatic Carboxylic Acid Derivatives.

A novel copper-catalyzed carbonylative trifluoromethylation of unactivated alkenes has been developed. A broad range of ß-trifluoromethylated carboxylic acid derivatives were prepared in moderate to excellent yields from simple alkenes with excellent regioselectivity. It is noteworthy that ethylene gas, as the simplest olefin, can also be applied directly to obtain ß-trifluoromethylated amides and ester. This transformation presents the first example on carbonylative trifluoromethylation of alkenes.

Copper-Catalyzed Borylative Methylation of Alkyl Iodides with CO as the C1 Source: Advantaged by Faster Reaction of CuH over CuBpin.

CuH and CuBpin are versatile catalysts and intermediates in organic chemistry. However, studies that involve both CuH and CuBpin in the same reaction is still rarely reported due to their high reactivity. Now, a study on CuH- and CuBpin-catalyzed borylative methylation of alkyl iodides with CO as the C1 source is reported. Various one carbon prolongated alkyl boranes (RCH2 Bpin and RCH(Bpin)2 ) were produced in moderate to good yields from the corresponding alkyl iodides (RI). In this cooperative system, CuH reacts with alkyl iodide faster than CuBpin.

Pd/Cu-Catalyzed Defluorinative Carbonylative Coupling of Aryl Iodides and gem-Difluoroalkenes: Efficient Synthesis of α-Fluorochalcones.

An unprecedented and challenging defluorinative carbonylation was achieved. Enabled by a Pd/Cu cooperative catalyst system, the first example of defluorinative carbonylative coupling has been established. With gem-difluoroalkenes and aryl iodides as the substrates, this methodology offers flexible and facile access to privileged α-fluorochalcones under mild reaction conditions in moderate-to-excellent yields. Mechanistic studies indicated transmetalation between palladium and copper intermediates as a crucial step of the catalytic cycle.

Copper-Catalyzed Synthesis of Stereodefined Cyclopropyl Bis(boronates) from Alkenes with CO as the C1 Source.

A novel copper-catalyzed stereodefined procedure for the selective synthesis of cyclopropyl bis(boronates) from terminal alkenes has been developed. Various aliphatic alkenes were transformed into the desired bis(boronate ester)-substituted cyclopropanes in moderate to good yields. Synthetic transformations of the resulting cyclopropyl bis(boronates) demonstrate their utility. A possible reaction mechanism is proposed.

Four-Component Borocarbonylation of Vinylarenes Enabled by Cooperative Cu/Pd Catalysis: Access to ß-Boryl Ketones and ß-Boryl Vinyl Esters.

We report here a general four-component synthetic procedure for the preparation of ß-boryl ketones and ß-boryl vinyl esters. Joint catalyzed by palladium and copper catalysts, borocarbonylative reaction between vinylarenes, aryl halides/triflates, B2 Pin2 , and carbon monoxide proceed successfully. A variety of synthetically useful ß-boryl ketones were synthesized in good to high yields by using aryl iodides as the substrates. It is noteworthy that when aryl triflates were applied as the starting materials, ß-boryl vinyl esters were synthesized in a similar manner and with broad functional group tolerance. A rational mechanism for this reaction was also proposed.

Copper-Catalyzed Carbonylative Hydroamidation of Styrenes to Branched Amides.

Amides are one of the most ubiquitous functional groups in synthetic and medicinal chemistry. Novel and rapid synthesis of amides remains in high demand. In this communication, a general and efficient procedure for branch-selective hydroamidation of vinylarenes with hydroxyamine derivatives enabled by copper catalysis has been developed for the first time. The reaction proceeds under mild conditions and tolerates a broad range of functional groups. Applying a chiral phosphine ligand, an enantioselective variant of this transformation was achieved, affording a variety of chiral α-amides with excellent enantioselectivities (up to 99 % ee) and high yields.

Copper-Catalyzed Regioselective Borocarbonylative Coupling of Unactivated Alkenes with Alkyl Halides: Synthesis of ß-Boryl Ketones.

The borocarbonylative coupling of unactivated alkenes with alkyl halides remains a challenge. In this communication, a Cu-catalyzed borocarbonylative coupling of unactivated alkenes with alkyl halides for the synthesis of ß-boryl ketones has been developed. A broad range of ß-boryl ketone derivatives was prepared in moderate to excellent yields with complete regioselectivity.

Palladium-Catalyzed Tunable Carbonylative Synthesis of Enones and Benzofulvenes.

A palladium-catalyzed four-component carbonylative coupling reaction involving aryl halides, internal alkynes, arylboronic acids, and CO has been developed for the first time. All-carbon substituted α-unsaturated ketones and benzofulvenes can be selectively obtained in a highly regio- and stereocontrolled manner. Using Cu(TFA)2 as the additive, a series of tetrasubstituted α-unsaturated ketones were prepared in moderate to high yields. Using more acidic Lewis acid Cu(OTf)2 as the additive, multisubstituted benzofluvenes were synthesized in moderate yields. This efficient methodology involved the formation of three new C-C bonds, and provided a divergent method for the quick construction of multisubstituted α-unsaturated ketones and benzofulvenes from easily available starting materials.

Deep-Blue and Hybrid-White Organic Light Emitting Diodes Based on a Twisting Carbazole-Benzofuro[2,3-b]Pyrazine Fluorescent Emitter.

A novel deep-blue fluorescent emitter was designed and synthesized. The external quantum efficiency (ηEQE) of the blue-emitting, doped, organic light-emitting diode (OLED) was as high as 4.34%. The device also exhibited an excellent color purity with Commission Internationale de l'Eclairage (CIE) coordinates of x = 0.15 and y = 0.05. In addition, the triplet energy had a value of 2.7 eV, which is rare for an emitter with deep-blue emission, which makes it a preferred choice for high-performance white OLEDs. By optimizing the device architectures, the color of hybrid-white OLEDs could be tunable from warm white to cool white using the aforementioned material as a bifunctional material. That is, the ηEQE of the hybrid warm-white OLED is 20.1% with a CIE x and y of 0.46 and 0.48 and the ηEQE of the hybrid cool-white OLED is 9% with a CIE x and y of 0.34 and 0.33.

Nickel-Catalyzed Molybdenum-Promoted Carbonylative Synthesis of Benzophenones.

A nickel-catalyzed molybdenum-promoted carbonylative coupling reaction for the synthesis of benzophenones from aryl iodides has been developed. Various substituted diaryl ketones were synthesized in moderate to excellent yields under CO-gas-free conditions. A synergetic effect of both nickel and molybdenum has been observed, which is also responsible for the success of this transformation.

An Imide-Based Pentacyclic Building Block for n-Type Organic Semiconductors.

A new electron-deficient unit with a fused 5-membered heterocyclic ring was developed by replacing a cyclopenta-1,3-diene from electron-rich donor indacenodithiophene (IDT) with a cyclohepta-4,6-diene-1,3-diimde unit. The imide bridge endows dithienylbenzenebisimide (BBI) with a fixed planar configuration and low energy levels for both the highest occupied molecular orbital (HOMO; -6.24 eV) and the lowest unoccupied molecular orbit (LUMO; -2.57 eV). Organic field-effect transistors (OFETs) based on BBI polymers exhibit electron mobility up to 0.34 cm2 V-1 s-1 , which indicates that the BBI is a promising n-type building block for optoelectronics.

Palladium-Catalyzed Carbonylative Transformation of Organic Halides with Formic Acid as the Coupling Partner and CO Source: Synthesis of Carboxylic Acids.

A palladium-catalyzed carbonylative transformation of organic halides with formic acid as the coupling partner to produce carboxylic acids has been developed. With a catalytic amount of DCC as the activator of formic acid, the process can be realized successfully through benzoic formic anhydride as the intermediate. Both vinyl and aryl (pseudo)halides were conveniently transformed into the corresponding acids in good yields.