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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.

The chelating ability of quinoxaline cores and the redox activity of organo-sulfide bridges in layered covalent-organic frameworks (COFs) offer dual active sites for reversible lithium (Li)-storage. The designed COFs combining these properties feature disulfide and polysulfide-bridged networks showcasing an intriguing lithium-storage mechanism, which can be considered as a lithium-organo-sulfide (Li-OrS) battery. The experimental-computational elucidation of three quinoxaline COFs containing systematically enhanced sulfur atoms in sulfide bridging demonstrates fast kinetics during Li interactions with the quinoxaline core. Meanwhile, bilateral covalent bonding of sulfide bridges to quinoxaline core enables a redox-mediated reversible cleavage of the sulfur-sulfur bond and the formation of covalently anchored lithium-sulfide chains or clusters during Li-interactions, accompanied by a marked reduction of Li-polysulfide (Li-PS) dissolution into the electrolyte, a frequent drawback of lithium-sulfur (Li-S) batteries. The electrochemical behavior of model compounds mimicking the sulfide linkages of the COFs and operando Raman studies on the framework structure unravels the reversibility of the profound Li-ion-organo-sulfide interactions. As a result, nearly 84% retention of specific capacity was observed at 100 mA/g for the polysulfide-bridged COF after 500 charge-discharge cycles. Thus, integrating redox-active organic-framework materials with covalently anchored sulfides enables a stable Li-OrS battery mechanism which shows benefits over a typical Li-S battery.

Two dimensional van der Waals heterostructures (2D are of significant interest due to their intriguing physical properties that are critically defined by the constituent monolayers and their interlayer coupling . However, typical inorganic 2 D vdWhs fall into the weakly coupled region, limiting efficient interfacial charge flow crucial for developing high performance quantum opto electronics. Here, we demonstrate strong interlayer coupling in Cu3 BHT (BHT = benzenehexathiol) graphene vdWhs an organic inorganic bilayer characterized by prominent interlayer charge transfer Monolayer Cu3 BHT with a Kagome lattice is synthesized on the water surface and then coupled with graphene to produce a cm2 scale 2D vdWh. Spectroscopic and electrical studies, along with theoretical calculation s show significant hole transfer from monolayer Cu3 BHT to graphene upon contact , being characteristic fingerprints for strong interlayer coupling This study unveils the great potential of integrating highly pi-conjugated 2D coordination polymers (2DCPs) into 2D vdWhs to explor e intriguing physical phenomena.

Conversion of light into heat is essential for a broad range of technologies such as solar thermal heating, catalysis and desalination. Three-dimensional (3D) carbon nanomaterial-based aerogels have shown to hold great promise as photothermal transducer materials. However, till now, their light-to-heat conversion is limited by surface-near absorption, resulting in a strong heat localization only at the illuminated surface region, while most of the aerogel volume remains unused. We present an innovative fabrication concept for highly porous (>99.9%) photothermal hybrid aeromaterials, that enable an ultra-rapid and volumetric photothermal response with an enhancement by a factor of around 2.5 compared to the pristine variant. The hybrid aeromaterial is based on strongly light-scattering framework structures composed of interconnected hollow silicon dioxide (SiO${_2}$) microtubes, which are functionalized with extremely low amounts (in order of a few ${\mu}$g cm${^-}$${^3}$) of reduced graphene oxide (rGO) nanosheets, acting as photothermal agents. Tailoring the density of rGO within the framework structure enables us to control both, light scattering and light absorption, and thus the volumetric photothermal response. We further show that by rapid and repeatable gas activation these transducer materials expand the field of photothermal applications, like untethered light-powered and -controlled microfluidic pumps and soft pneumatic actuators.

Hydrogel-based soft actuators can operate in sensitive environments, bridging the gap of rigid machines interacting with soft matter. However, while stimuli-responsive hydrogels can undergo extreme reversible volume changes of up to ~90%, water transport in hydrogel actuators is in general limited by their poroelastic behavior. For poly(N-isopropylacrylamide) (PNIPAM) the actuation performance is even further compromised by the formation of a dense skin layer. Here we show, that incorporating a bioinspired microtube graphene network into a PNIPAM matrix with a total porosity of only 5.4 % dramatically enhances actuation dynamics by up to ~400 % and actuation stress by ~4000 % without sacrificing the mechanical stability, overcoming the water transport limitations. The graphene network provides both untethered light-controlled and electrically-powered actuation. We anticipate that the concept provides a versatile platform for enhancing the functionality of soft matter by combining responsive and two-dimensional materials, paving the way towards designing soft intelligent matter., Comment: Shared First-authorship: Margarethe Hauck and Lena Marie Saure

Quasi-two-dimensional conjugated polymers (q2DCPs) are polymers that consist of linear conjugated polymer chains assembled through non-covalent interactions to form a layered structure. In this work, w e report the synthesis of a novel crystalline q2D polypyrrole (q2DPPy) film at an air/H2 SO4 (95%) interface. The unique interfacial environment facilitated chain extension, prevented disorder, and resulted in a crystalline, layered assembly of protonated quinoidal chains with a fully extended conformation in its crystalline domains. This unique structure features highly delocalized π-electron systems within the extended chains, which is responsible for the low effective mass and narrow electronic bandgap. Thus w e investigated the temperature-dependent charge transport properties of q2DPPy using the van der Pauw (vdP) method and terahertz time-domain spectroscopy (THz-TDS). The vdP method revealed that the q2DPPy film exhibited a semiconducting behavior with a thermally activated hopping mechanism in long-range transport between the electrodes. Conversely, THz-TDS revealed a band-like transport, indicating intrinsic charge transport up to a record short-range high THz mobility of ∼107.1 cm2 V-1 s-1 . This article is protected by copyright. All rights reserved.

Heterogeneous reactions associated with porous solid films are ubiquitous and play an important role in both nature and industrial processes. However, due to the no-slip boundary condition in pressure-driven flows, the interfacial mass transfer between the porous solid surface and the environment is largely limited to slow molecular diffusion, which severely hinders the enhancement of heterogeneous reaction kinetics. Herein, we report a hierarchical-structure-accelerated interfacial dynamic strategy to improve interfacial gas transfer on hierarchical conductive metal-organic framework (c-MOF) films. Hierarchical c-MOF films are synthesized via the in-situ transformation of insulating MOF film precursors using π-conjugated ligands and comprise both a nanoporous shell and hollow inner voids. The introduction of hollow structures in the c-MOF films enables an increase of gas permeability, thus enhancing the motion velocity of gas molecules toward the c-MOF film surface, which is more than 8.0-fold higher than that of bulk-type film. The c-MOF film-based chemiresistive sensor exhibits a faster response towards ammonia than other reported chemiresistive ammonia sensors at room temperature and a response speed 10 times faster than that of the bulk-type film.

UNLABELLED On-surface synthesis is a rapidly developing field involving chemical reactions on well-defined solid surfaces to access synthesis of low-dimensional organic nanostructures which cannot be achieved via traditional solution chemistry. On-surface reactions critically depend on a high degree of chemoselectivity in order to achieve an optimum balance between target structure and possible side products. Here, we demonstrate synthesis of graphene nanoribbons with a large unit cell based on steric hindrance-induced complete chemoselectivity as revealed by scanning probe microscopy measurements and density functional theory calculations. Our results disclose that combined molecule-substrate van der Waals interactions and intermolecular steric hindrance promote a selective aryl-aryl coupling, giving rise to high-quality uniform graphene nanostructures. The established coupling strategy has been used to synthesize two types of graphene nanoribbons with different edge topologies inducing a pronounced variation of the electronic energy gaps. The demonstrated chemoselectivity is representative for n-anthryl precursor molecules and may be further exploited to synthesize graphene nanoribbons with novel electronic, topological and magnetic properties with implications for electronic and spintronic applications. SUPPLEMENTARY INFORMATION The online version contains supplementary material available at 10.1007/s44214-022-00023-9.