Dicyclopentaannelated Hexa-peri-hexabenzocoronenes with a Singlet Biradical Ground State.

Synthesis of two dicyclopentaannelated hexa-peri-hexabenzocoronene (PHBC) regioisomers was carried out, using nonplanar oligoaryl precursors with fluorenyl groups: mPHBC 8 with two pentagons in the "meta"-configuration was obtained as a stable molecule, while its structural isomer with the "para"-configuration, pPHBC 16, could be generated and characterized only in situ due to its high chemical reactivity. Both PHBCs exhibit low energy gaps, as reflected by UV-vis-NIR absorption and electrochemical measurements. They also show open-shell singlet ground states according to electron paramagnetic resonance (EPR) measurements and density functional theory (DFT) calculations. The use of fully benzenoid HBC as a bridging moiety leads to significant singlet biradical characters (y0 ) of 0.72 and 0.96 for mPHBC 8 and pPHBC 16, respectively, due to the strong rearomatization tendency of the HBC π-system; these values are among the highest for planar carbon-centered biradical molecules. The incorporation of fully unsaturated pentagons strongly perturbs the aromaticity of the parent HBC and makes the constituted benzene rings less aromatic or antiaromatic. These results illustrate the high impact of cyclopentaannelation on the electronic structures of fully benzenoid polycyclic aromatic hydrocarbons (PAHs) and open up a new avenue towards open-shell PAHs with prominent singlet biradical characters.

On-Surface Synthesis of Unsaturated Carbon Nanostructures with Regularly Fused Pentagon-Heptagon Pairs.

Multiple fused pentagon-heptagon pairs are frequently found as defects at the grain boundaries of the hexagonal graphene lattice and are suggested to have a fundamental influence on graphene-related materials. However, the construction of sp2-carbon skeletons with multiple regularly fused pentagon-heptagon pairs is challenging. In this work, we found that the pentagon-heptagon skeleton of azulene was rearranged during the thermal reaction of an azulene-incorporated organometallic polymer on Au(111). The resulting sp2-carbon frameworks were characterized by high-resolution scanning probe microscopy techniques and feature novel polycyclic architectures composed of multiple regularly fused pentagon-heptagon pairs. Moreover, the calculated analysis of its aromaticity revealed a peculiar polar electronic structure.

Proton-Gated Ring-Closure of a Negative Photochromic Azulene-Based Diarylethene.

Proton-responsive photochromic molecules are attractive for their ability to react on non-invasive rapid optical stimuli and the importance of protonation/deprotonation processes in various fields. Conventionally, their acidic/basic sites are on hetero-atoms, which are orthogonal to the photo-active π-center. Here, we incorporate azulene, an acid-sensitive pure hydrocarbon, into the skeleton of a diarylethene-type photoswitch. The latter exhibits a novel proton-gated negative photochromic ring-closure and its optical response upon protonation in both open and closed forms is much more pronounced than those of diarylethene photoswitches with hetero-atom based acidic/basic moieties. The unique behavior of the new photoswitch can be attributed to direct protonation on its π-system, supported by 1H NMR and theoretical calculations. Our results demonstrate the great potential of integrating non-alternant hydrocarbons into photochromic systems for the development of multi-responsive molecular switches.

Edge Functionalization of Structurally Defined Graphene Nanoribbons for Modulating the Self-Assembled Structures.

Edge functionalization of bottom-up synthesized graphene nanoribbons (GNRs) with anthraquinone and naphthalene/perylene monoimide units has been achieved through a Suzuki coupling of polyphenylene precursors bearing bromo groups, prior to the intramolecular oxidative cyclo-dehydrogenation. High efficiency of the substitution has been validated by MALDI-TOF MS analysis of the functionalized precursors and FT-IR, Raman, and XPS analyses of the resulting GNRs. Moreover, AFM measurements demonstrated the modulation of the self-assembling behavior of the edge-functionalized GNRs, revealing that GNR-PMI formed an intriguing rectangular network. This result suggests the possibility of programming the supramolecular architecture of GNRs by tuning the functional units.

Orthogonal analysis of variants in APOE gene using in-silico approaches reveals novel disrupting variants.

Introduction: Alzheimer's disease (AD) is one of the most prominent medical conditions in the world. Understanding the genetic component of the disease can greatly advance our knowledge regarding its progression, treatment and prognosis. Single amino-acid variants (SAVs) in the APOE gene have been widely investigated as a risk factor for AD Studies, including genome-wide association studies, meta-analysis based studies, and in-vivo animal studies, were carried out to investigate the functional importance and pathogenesis potential of APOE SAVs. However, given the high cost of such large-scale or experimental studies, there are only a handful of variants being reported that have definite explanations. The recent development of in-silico analytical approaches, especially large-scale deep learning models, has opened new opportunities for us to probe the structural and functional importance of APOE variants extensively. Method: In this study, we are taking an ensemble approach that simultaneously uses large-scale protein sequence-based models, including Evolutionary Scale Model and AlphaFold, together with a few in-silico functional prediction web services to investigate the known and possibly disease-causing SAVs in APOE and evaluate their likelihood of being functional and structurally disruptive. Results: As a result, using an ensemble approach with little to no prior field-specific knowledge, we reported 5 SAVs in APOE gene to be potentially disruptive, one of which (C112R) was classificed by previous studies as a key risk factor for AD. Discussion: Our study provided a novel framework to analyze and prioritize the functional and structural importance of SAVs for future experimental and functional validation.

Synthesis of Giant Dendritic Polyphenylenes with 366 and 546 Carbon Atoms and Their High-vacuum Electrospray Deposition.

Dendritic polyphenylenes (PPs) can serve as precursors of nanographenes (NGs) if their structures represent 2D projections without overlapping benzene rings. Here, we report the synthesis of two giant dendritic PPs fulfilling this criteria with 366 and 546 carbon atoms by applying a "layer-by-layer" extension strategy. Although our initial attempts on their cyclodehydrogenation toward the corresponding NGs in solution were unsuccessful, we achieved their deposition on metal substrates under ultrahigh vacuum through the electrospray technique. Scanning probe microscopy imaging provides valuable information on the possible thermally induced partial planarization of such giant dendritic PPs on a metal surface.

On-surface synthesis of polyazulene with 2,6-connectivity.

Azulene, the smallest neutral nonalternant aromatic hydrocarbon, serves not only as a prototype for fundamental studies but also as a versatile building block for functional materials because of its unique opto(electronic) properties. Here, we report the on-surface synthesis and characterization of the homopolymer of azulene connected exclusively at the 2,6-positions using 2,6-diiodoazulene as the monomer precursor. As an intermediate to the formation of polyazulene, a gold-(2,6-azulenylene) chain is observed.

Chemisorption of Atomically Precise 42-Carbon Graphene Quantum Dots on Metal Oxide Films Greatly Accelerates Interfacial Electron Transfer.

Graphene quantum dots (GQDs) are emerging as environmentally friendly, low-cost, and highly tunable building blocks in solar energy conversion architectures, such as solar (fuel) cells. Specifically, GQDs constitute a promising alternative for organometallic dyes in sensitized oxide systems. Current sensitized solar cells employing atomically precise GQDs are based on physisorbed sensitizers, with typically limited efficiencies. Chemisorption has been pointed out as a solution to boost photoconversion efficiencies, by allowing improved control over sensitizer surface coverage and sensitizer-oxide coupling strength. Here, employing time-resolved THz spectroscopy, we demonstrate that chemisorption of atomically precise C42-GQDs (hexa- peri-hexabenzocoronene derivatives consisting of 42 sp2 carbon atoms) onto mesoporous metal oxides, enabled by their functionalization with a carboxylate group, enhances electron transfer (ET) rates by almost 2 orders of magnitude when compared with physisorbed sensitizers. Density functional theory (DFT) calculations, absorption spectroscopy and valence band X-ray photoelectron spectroscopy reveal that the enhanced ET rates can be traced to stronger donor-acceptor coupling strength enabled by chemisorption.

Hexa-peri-hexabenzocoronene with Different Acceptor Units for Tuning Optoelectronic Properties.

Hexa-peri-hexabenzocoronene (HBC)-based donor-acceptor dyads were synthesized with three different acceptor units, through two pathways: 1) "pre-functionalization" of monobromo-substituted hexaphenylbenzene prior to the cyclodehydrogenation; and 2) "post-functionalization" of monobromo-substituted HBC after the cyclodehydrogenation. The HBC-acceptor dyads demonstrated varying degrees of intramolecular charge-transfer interactions, depending on the attached acceptor units, which allowed tuning of their photophysical and optoelectronic properties, including the energy gaps. The two synthetic pathways described here can be complementary and potentially be applied for the synthesis of nanographene-acceptor dyads with larger aromatic cores, including one-dimensionally extended graphene nanoribbons.