Pushing Up the Size Limit of Boron-doped peri-Acenes: Modular Synthesis and Characterizations.

Heteroatom-doped peri-acenes (PAs) have recently attracted considerable attention considering their fascinating physical properties and chemical stability. However, the precise sole addition of boron atoms along the zigzag edges of PAs remains challenging, primarily due to the limited synthetic approach. Herein, we present a novel one-pot modular synthetic strategy toward unprecedented boron-doped PAs (B-PAs), including B-[4,2]PA (1 a-2), B-[4,3]PA (1 b-2) and B-[7,2]PA (1 c-3) derivatives, through efficient intramolecular electrophilic borylation. Their chemical structures are unequivocally confirmed with a combination of mass spectrometry, NMR, and single-crystal X-ray diffraction analysis. Notably, 1 b-2 exhibits an almost planar geometry, whereas 1 a-2 displays a distinctive bowl-like distortion. Furthermore, the optoelectronic properties of this series of B-PAs are thoroughly investigated by UV/Vis absorption and fluorescence spectroscopy combined with DFT calculation. Compared with their parent all-carbon analogs, the obtained B-PAs exhibit high stability, wide energy gaps, and high photoluminescence quantum yields of up to 84 %. This study reveals the exceptional ability of boron doping to finely tune the physicochemical properties of PAs, showcasing their potential applications in optoelectronics.

Precision Graphene Nanoribbon Heterojunctions by Chain-Growth Polymerization.

Graphene nanoribbons (GNRs) are considered promising candidates for next-generation nanoelectronics. In particular, GNR heterojunctions have received considerable attention due to their exotic topological electronic phases at the heterointerface. However, strategies for their precision synthesis remain at a nascent stage. Here, we report a novel chain-growth polymerization strategy that allows for constructing GNR heterojunction with N=9 armchair and chevron GNRs segments (9-AGNR/cGNR). The synthesis involves a controlled Suzuki-Miyaura catalyst-transfer polymerization (SCTP) between 2-(6'-bromo-4,4''-ditetradecyl-[1,1':2',1''-terphenyl]-3'-yl) boronic ester (M1) and 2-(7-bromo-9,12-diphenyl-10,11-bis(4-tetradecylphenyl)-triphenylene-2-yl) boronic ester (M2), followed by the Scholl reaction of the obtained block copolymer (poly-M1/M2) with controlled Mn (18 kDa) and narrow D (1.45). NMR and SEC analysis of poly-M1/M2 confirm the successful block copolymerization. The solution-mediated cyclodehydrogenation of poly-M1/M2 toward 9-AGNR/cGNR is unambiguously validated by FT-IR, Raman, and UV/Vis spectroscopies. Moreover, we also demonstrate the on-surface formation of pristine 9-AGNR/cGNR from the unsubstituted copolymer precursor, which is unambiguously characterized by scanning tunneling microscopy (STM).

Single-cell genetic models to evaluate orphan gene function: The case of QQS regulating carbon and nitrogen allocation.

We demonstrate two synthetic single-cell systems that can be used to better understand how the acquisition of an orphan gene can affect complex phenotypes. The Arabidopsis orphan gene, Qua-Quine Starch (QQS) has been identified as a regulator of carbon (C) and nitrogen (N) partitioning across multiple plant species. QQS modulates this important biotechnological trait by replacing NF-YB (Nuclear Factor Y, subunit B) in its interaction with NF-YC. In this study, we expand on these prior findings by developing Chlamydomonas reinhardtii and Saccharomyces cerevisiae strains, to refactor the functional interactions between QQS and NF-Y subunits to affect modulations in C and N allocation. Expression of QQS in C. reinhardtii modulates C (i.e., starch) and N (i.e., protein) allocation by affecting interactions between NF-YC and NF-YB subunits. Studies in S. cerevisiae revealed similar functional interactions between QQS and the NF-YC homolog (HAP5), modulating C (i.e., glycogen) and N (i.e., protein) allocation. However, in S. cerevisiae both the NF-YA (HAP2) and NF-YB (HAP3) homologs appear to have redundant functions to enable QQS and HAP5 to affect C and N allocation. The genetically tractable systems that developed herein exhibit the plasticity to modulate highly complex phenotypes.

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.

Helical Bilayer Nonbenzenoid Nanographene Bearing a [10]Helicene with Two Embedded Heptagons.

The precision synthesis of helical bilayer nanographenes (NGs) with new topology is of substantial interest because of their exotic physicochemical properties. However, helical bilayer NGs bearing non-hexagonal rings remain synthetically challenging. Here we present the efficient synthesis of the first helical bilayer nonbenzenoid nanographene (HBNG1) from a tailor-made azulene-embedded precursor, which contains a novel [10]helicene backbone with two embedded heptagons. Single-crystal X-ray analysis reveals its highly twisted bilayer geometry with a record small interlayer distance of 3.2 Šamong the reported helical bilayer NGs. Notably, the close interlayer distance between the two layers offers intramolecular through-space conjugation as revealed by in situ spectroelectrochemistry studies together with DFT simulations. Furthermore, the chiroptical properties of the P/M enantiomers of HBNG1 are also evaluated by circular dichroism and circularly polarized luminescence.

Large Acene Derivatives with B-N Lewis Pair Doping: Synthesis, Characterization, and Application.

Here, we report the synthesis of a novel class of B-N Lewis pair (LPB/N)-doped large acene derivatives (1a-1d) from the well-designed phenanthridine-based precursors. The resultant LPB/N-doped benzo-tetracene (1a), dibenzo-heptacene (1b), dibenzo-octacene (1c), and V-shaped tribenzo-nonacene (1d) are thoroughly characterized by X-ray crystallography, cyclic voltammetry, UV-vis absorption, and fluorescence spectroscopies together with DFT calculations. As a proof of concept, a 1a-based organic light-emitting diode device is fabricated to demonstrate the promising application in organic optoelectronics.

A Modular Cascade Synthetic Strategy Toward Structurally Constrained Boron-Doped Polycyclic Aromatic Hydrocarbons.

A novel synthetic strategy was developed for the construction of difficult-to-access structurally constrained boron-doped polycyclic aromatic hydrocarbons (sc-B-PAHs) via a cascade reaction from the readily available ortho-aryl-substituted diarylalkynes. This domino process involves borylative cyclization, 1,4-boron migration and successive two-fold electrophilic borylation. Two types of sc-B-PAHs bearing B-doped [4]helicene (1 a-1 i) or BN-doped [4]helicene (1 n-1 t) and double [4]helicene (1 u-1 v) are constructed by this cascade reaction. Remarkably, this synthetic strategy is characterized by modest yields (20-50 %) and broad substrate scope (18 examples) with versatile functional group tolerance. The resultant sc-B-PAHs show good stability under ambient conditions and are thoroughly investigated by X-ray crystallography, UV/Vis absorption and fluorescence spectroscopy, and cyclic voltammetry. Interestingly enough, BN-doped [4]helicene 1 o forms a unique alternating π-stacked dimer of enantiomers within a helical columnar superstructure, while BN-doped double [4]helicene 1 u establishes an unprecedented π-stacked trimeric sandwich structure with a rare 2D lamellar π-stacking. The synthetic approach reported herein represents a powerful tool for the rapid generation of novel sc-B-PAHs, which are highly attractive for the elucidation of the structure-property relationship and for potential optoelectronic applications.

One-Pot Synthesis of Boron-Doped Polycyclic Aromatic Hydrocarbons via 1,4-Boron Migration.

Herein, we demonstrate a novel one-pot synthetic method towards a series of boron-doped polycyclic aromatic hydrocarbons (B-PAHs, 1 a-1 o), including hitherto unknown B-doped zethrene derivatives, from ortho-aryl substituted diarylalkynes with high atom efficiency and broad substrate scopes. A reaction mechanism is proposed based on the experimental investigation together with the theoretical calculations, which involves a unique 1,4-boron migration process. The resultant benchtop-stable B-PAHs are thoroughly investigated by X-ray crystallography, cyclic voltammetry, UV/Vis absorption, and fluorescence spectroscopies. The blue and green organic light-emitting diode (OLED) devices based on 1 f and 1 k are further fabricated, demonstrating the promising application potential of B-PAHs in organic optoelectronics.

Nonzero Wavevector Excitation of Graphene by Localized Surface Plasmons.

Electrochemical surface-enhanced Raman scattering measurements of single layer graphene provide unique information on resonant excitation induced by localized surface plasmons under controlled electron or hole doping. The highly confined electromagnetic field from the LSPs of the Au nanodimer structures prepared on defect-free graphene can generate holes and electrons of the electrochemical potentials beyond the limit of far-field light illumination. The electrochemical in situ SERS spectra prove nonzero wavevector excitation through the observation of normally forbidden Raman bands in graphene. The present findings point to a novel approach to breaking the limit of optoelectronic interactions and photochemical reactions of graphene and other semiconductors.

Transition-metal free C-C bond cleavage/borylation of cycloketone oxime esters.

An efficient transition-metal free C-C bond cleavage/borylation of cycloketone oxime esters has been described. In this reaction, the B2(OH)4 reagent not only served as the boron source but also acted as an electron donor source through formation of a complex with a DMAc-like Lewis base. This complex could be used as an efficient single electron reductant in other ring-opening transformations of cycloketone oxime esters. Free-radical trapping, radical-clock, and DFT calculations all suggest a radical pathway for this transformation.

Metal-Free, Visible-Light-Promoted Decarboxylative Radical Cyclization of Vinyl Azides with N-Acyloxyphthalimides.

A visible-light-mediated decarboxylative cyclization of N-acyloxylphthalimides with vinyl azides has been developed under metal-free conditions. This protocol features mild conditions, a broad substrate scope, and an excellent functional group tolerance, thus providing a facile and efficient access to substituted phenanthridines. Control experiments revealed that the reaction proceeded via a radical process.

Visible-Light-Mediated Dual Decarboxylative Coupling of Redox-Active Esters with α,ß-Unsaturated Carboxylic Acids.

An efficient visible-light-induced decarboxylative coupling between α,ß-unsaturated carboxylic acids and alkyl N-hydroxyphthalimide esters has been developed. A wide range of redox-active esters derived from aliphatic carboxylic acids (1°, 2° and 3°) proved viable in this dual decarboxylation process, affording a broad scope of substituted alkenes in moderate to excellent yields with good E/Z selectivities. This redox-neutral procedure was highlighted by its mild conditions, operational simplicity, easy accessibility of carboxylic acids, and excellent functional-group tolerance.

Copper-catalyzed oxidative cyclization of vinyl azides with benzylic Csp3-H bonds for the synthesis of substituted phenanthridines.

A copper-catalyzed oxidative cyclization of vinyl azides with benzylic Csp3-H bonds via a tandem dual C-H functionalization process has been developed. This procedure allows access to substituted phenanthridines containing a variety of functional groups. In addition to benzyl hydrocarbons, other substrates containing unactivated Csp3-H bonds, such as ethers and alkanes could also be applied successfully to this transformation.

A theoretical study of asymmetric electron transport through linearly aromatic molecules.

Electron transport through a series of polyacene molecules connected via a π-conjugated bridge (an anthracene molecule) was investigated theoretically by using the nonequilibrium Green's function formalism combined with density functional theory. The results have shown that the asymmetric current-voltage characteristics can be achieved by tuning the position of a side π-bridge linked to the main conjugated backbone. The detailed analyses of the spatial distribution of molecular orbitals as well as the current density interpret how the location of π-bridge strongly affects the intramolecular electronic coupling. The rectification in the molecular junction arises from the localization of the molecular orbitals near the Fermi level and the asymmetric shift of molecule orbital energy levels under positive and negative bias. The rectification ratio decreases with increasing the length of the π-bridge which improves intramolecular electronic coupling between aromatic rings. Furthermore, the rectification properties of conjugated molecules are just slightly affected by the anchoring positions of thiol groups. These results demonstrated that the location and the length of π-bridge, which induce the asymmetric intramolecular coupling, play key roles in the rectification of the linearly aromatic molecules.