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We report a rapid, room-temperature mechanochemical synthesis of 2- and 3-dimensional boroxine covalent organic frameworks (COFs), enabled by using trimethylboroxine as a dehydrating additive to overcome the hydrolytic sensitivity of boroxine-based COFs. The resulting COFs display high porosity and crystallinity, with COF-102 being the first example of a mechanochemically prepared 3D COF, exhibiting a surface area of ca. 2,500 m 2  g -1 . Mechanochemistry enabled a>20-fold reduction in solvent use and ~100-fold reduction in reaction time compared with solvothermal methods, providing target COFs quantitatively with no additional work-up besides vacuum drying. Real-time Raman spectroscopy permitted the first quantitative kinetic analysis of COF mechanosynthesis, while transferring the reaction design to Resonant Acoustic Mixing (RAM) enabled synthesis of multi-gram amounts of the target COFs (tested up to 10 g)., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Two near-infrared (NIR) emissive π-conjugated covalent organic frameworks (COFs) pTANG1 and pTANG2 are synthesized using Knoevenagel condensation of trioxaazatriangulenetricarbaldehyde (TATANG) with benzene- and biphenyldiacetonitriles, respectively. The morphology of the COFs is affected by the size of TATANG precursor crystals. Donor-acceptor interactions in these COFs result in small bandgaps (≈1.6 eV) and NIR emission (λ max = 789 nm for pTANG1). pTANG1 can absorb up to 9 molecules of water per unit cell, which is accompanied by a marked quenching of the NIR emission, suggesting applications as humidity sensors. p-Doping with magic blue significantly increases the electrical conductivities of the COFs by up to 8 orders of magnitude, with the room temperature conductivity of pTANG1 reaching 0.65 S cm -1 , the highest among reported C═C linked COFs. 1 H NMR relaxometry, temperature-dependent fluorescence spectroscopy, and DFT calculations reveal that the higher rigidity of the shorter phenylene linker is responsible for the more extended conjugation (red-shifted emission, higher electrical conductivity) of pTANG1 compared to pTANG2., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Ullmann coupling is a widely used reaction for the on-surface growth of low-dimensional carbon nanomaterials. The irreversible nature of this reaction prevents the "self-healing" of defects, and a detailed knowledge of its mechanism is therefore essential to enable the growth of extended ordered structures. However, the dynamics of the Ullmann polymerization remain largely unexplored, as coupling events occur on a timescale faster than conventional scanning probe microscopy imaging frequencies. Here, we reveal the dynamics of these surface events using high-speed variable-temperature scanning tunneling microscopy (STM) (10 frames per second). Performing the measurements at the onset reaction temperatures provides an unprecedented description of the evolution of organometallic (OM) and covalent surface species during the Ullmann polymerization of para -dibromobenzene on Cu(110). Our results demonstrate the existence of an intermediate OM phase with Cu adatoms that inhibits the polymerization. These observations now complete the picture of the pathways of on-surface Ullmann polymerization, which includes the complex interplay of the phenylene moieties and metal atoms. Our work demonstrates the unique capability of high-speed STM to capture the dynamics of molecular self-assembly and coupling.

Hydrogen-bonded (H-bonded) self-assembly is a suitable approach for tailoring the solid-state packing and properties of organic semiconductors. Here we studied the H-bonded self-assembly of an important class of organic semiconductors, diketopyrrolopyrrole (DPP) derivatives, diselenophenylDPP (DSeDPP), dithiazolylDPP (DTzDPP), and dithienothiophenylDPP (DTTDPP), at solid-liquid interfaces using scanning tunneling microscopy (STM) and density functional theory (DFT). At the 1-octanoic acid/highly ordered pyrolytic graphite (HOPG) interface, DSeDPP and DTzDPP either co-assemble with the solvent via H-bonding between lactam and carboxyl groups or form homoassemblies through H-bonding between the lactam groups. However, DTTDPP forms two different homoassemblies involving H-bonding between lactam groups or weak H-bonding between the lactam group and the heteroaromatic ring. Enthalpic factors for the formation of homoassemblies and co-assemblies are investigated by evaluating the inter- and intramolecular interactions in the self-assembled lattices using DFT. A homoassembly with a twisted geometry of molecules with intermolecular π-interactions is only observed for DSeDPP. The absence of homoassembly with the twisted geometry of DTzDPP is attributed to the higher strain energy required to acquire out-of-plane twists in this molecule. Our study shows the profound effects aromatic substituents can impart in the supramolecular assembly of DPP molecules, which influences film morphology and hence its properties ( e.g. charge transport).

Colloidal quantum dots (QDs) hold great promise as building blocks in solar technologies owing to their remarkable photostability and adjustable properties through the rationale involving size, atomic composition of core and shell, shapes, and surface states. However, most high-performing QDs in solar conversion contain hazardous metal elements, including Cd and Pb, posing significant environmental risks. Here, a comprehensive review of heavy-metal-free colloidal QDs for solar technologies, including photovoltaic (PV) devices, solar-to-chemical fuel conversion, and luminescent solar concentrators (LSCs), is presented. Emerging synthetic strategies to optimize the optical properties by tuning the energy band structure and manipulating charge dynamics within the QDs and at the QDs/charge acceptors interfaces, are analyzed. A comparative analysis of different synthetic methods is provided, structure-property relationships in these materials are discussed, and they are correlated with the performance of solar devices. This work is concluded with an outlook on challenges and opportunities for future work, including machine learning-based design, sustainable synthesis, and new surface/interface engineering., (© 2024 Wiley‐VCH GmbH.)

We report here that methyl-substituted hexamethoxytrityl (HMT) and the derived trioxatriangulene (TOTA) salts react with aldehydes, forming π-extended tristyryl-substituted HMT and TOTA dyes via a dynamic Knoevenagel condensation. These cations undergo a reversible electrochemical (or chemical) reduction, forming neutral radicals, including the first persistent TOTA radical. This reaction represents a promising platform to generate novel π-conjugated systems.

Quantum dots (QDs) are promising building blocks for luminescent solar concentrators (LSCs), yet most QD-based LSCs suffer from toxic metal composition and color tinting. UV-selective harvesting QDs can enable visible transparency, but their development is restricted by large reabsorption losses and low photoluminescence quantum yield (PLQY). The developed here Ag, Mn: ZnInS 2 /ZnS QDs show a high PLQY of 53% due to the passivating effect of ZnS shell. These QDs selectively absorb UV light and emit orange-red light with a large Stokes shift of 180 nm. A LSC of 5 × 5 × 0.2 cm 3 , fabricated using a poly(lauryl methacrylate) (PLMA) as a matrix, maintains 87% of integrated PL after 7 h of UV exposure. The QD-PLMA achieved 90.7% average visible transparency (AVT) and a color rendering index (CRI) of 95.8, which is close to plain PLMA (AVT = 90.8%; CRI = 99.5), yielding excellent visible light transparency. Incorporating Si-PVs at LSC edges, the Ag, Mn: ZIS/ZnS QD-LSC achieved an optical efficiency of 1.42%, ranking competitively among high-performing UV-harvesting LSCs., (© 2024 The Authors. Small Methods published by Wiley‐VCH GmbH.)

Despite enormous interest in two-dimensional (2D) carbon allotropes, discovering stable 2D carbon structures with practically useful electronic properties presents a significant challenge. Computational modeling in this work shows that fusing azulene-derived macrocycles - azulenoid kekulenes (AK) - into graphene leads to the most stable 2D carbon allotropes reported to date, excluding graphene. Density functional theory predicts that placing the AK units in appropriate relative positions in the graphene lattice opens the 0.54 eV electronic bandgap and leads to the appearance of the remarkable 0.80 eV secondary gap between conduction bands - a feature that is rare in 2D carbon allotropes but is known to enhance light absorption and emission in 3D semiconductors. Among porous AK structures, one material stands out as a stable narrow-multigap (0.36 and 0.56 eV) semiconductor with light charge carriers (m e  = 0.17 m 0 ,  m h  = 0.19 m 0 ), whereas its boron nitride analog is a wide-multigap (1.51 and 0.82 eV) semiconductor with light carriers (m e  = 0.39 m 0 ,  m h  = 0.32 m 0 ). The multigap engineering strategy proposed here can be applied to other carbon nanostructures creating novel 2D materials for electronic and optoelectronic applications., (© 2024. The Author(s).)

Thick-shell colloidal quantum dots (QDs) are promising building blocks for solar technologies due to their size/composition/shape-tunable properties. However, most well-performed thick-shell QDs suffer from frequent use of toxic metal elements including Pb and Cd, and inadequate light absorption in the visible and near-infrared (NIR) region due to the wide bandgap of the shell. In this work, eco-friendly AgInSe 2 /AgInS 2 core/shell QDs, which are optically active in the NIR region and are suitable candidates to fabricate devices for solar energy conversion, are developed. Direct synthesis suffers from simultaneously controlling the reactivity of multiple precursors, instead, a template-assisted cation exchange method is used. By modulating the monolayer growth of template QDs, gradient AgInSeS shell layers are incorporated into AgInSe 2 /AgInS 2 QDs. The resulting AgInSe 2 /AgInSeS/AgInS 2 exhibits better charge transfer than AgInSe 2 /AgInS 2 due to their favorable electronic band alignment, as predicted by first-principle calculations and confirmed by transient fluorescence spectroscopy. The photoelectrochemical cells fabricated with AgInSe 2 /AgInSeS/AgInS 2 QDs present ≈1.5-fold higher current density and better stability compared to AgInSe 2 /AgInS 2 . The findings define a promising approach toward multinary QDs and pave the way for engineering the QDs' electronic band structures for solar-energy conversion., (© 2023 The Authors. Small Methods published by Wiley-VCH GmbH.)

Catalytic electron donor-acceptor (EDA) complexes have recently emerged as a powerful and sustainable alternative to iridium- and ruthenium-based photoredox synthetic methods. Yet, these complexes remain underexplored and reliant on the use of meticulously designed acceptors that require previous installation. Herein, we report a novel EDA complex employing tris(4-methoxyphenyl) amine as a catalytic donor for the sulfonylation of alkenes using inexpensive and readily available sulfonyl chlorides. Applying this operationally simple, visible-light-mediated general platform, we report both the redox-neutral and net-reductive functionalization of more than 60 substrates, encompassing vinylic or allylic sulfonylation, hydrosulfonylation, and sulfamoylation of activated and unactivated alkenes and alkynes.

Two-dimensional conjugated polymers (2DCPs) are an emerging class of materials that exhibit properties similar to graphene yet do not have the limitation of zero bandgap. On-surface synthesis provides exceptional control on the polymerization reaction, allowing tailoring properties by choosing suitable monomers. Heteroatom-substituted triangulene 2DCPs constitute a playing ground for such a design and are predicted to exhibit graphene-like band structures with high charge mobility and characteristic Dirac cones in conduction or valence states. However, measuring these properties experimentally is challenging and requires long-range-ordered polymers, preferably with an epitaxial relationship with the substrate. Here, we investigate the electronic properties of a mesoscale-ordered carbonyl-bridged triphenylamine 2DCP (P 2 TANGO) and demonstrate the presence of a Dirac cone by combining angle-resolved photoemission spectroscopy (ARPES) with density functional theory (DFT) calculations. Moreover, we measure the absolute energy position of the Dirac cone with respect to the vacuum level. We show that the bridging functionality of the triangulene (ether vs carbonyl) does not significantly perturb the band structure but strongly affects the positioning of the bands with respect to the Au(111) states and allows control of the ionization energy of the polymer. Our results provide proof of the controllable electronic properties of 2DCPs and bring us closer to their use in practical applications.

Carbon, although the central element in organic chemistry, has been traditionally neglected as a target for directional supramolecular interactions. The design of supramolecular structures involving carbon-rich molecules, such as arene hydrocarbons, has been limited almost exclusively to non-directional π-stacking, or derivatisation with heteroatoms to introduce molecular assembly recognition sites. As a result, the predictable assembly of non-derivatised, carbon-only π-systems using directional non-covalent interactions remains an unsolved fundamental challenge of solid-state supramolecular chemistry. Here, we propose and validate a different paradigm for the reliable assembly of carbon-only aromatic systems into predictable supramolecular architectures: not through non-directional π-stacking, but via specific and directional halogen bonding. We present a systematic experimental, theoretical and database study of halogen bonds to carbon-only π-systems (C-I⋯π C bonds), focusing on the synthesis and structural analysis of cocrystals with diversely-sized and -shaped non-derivatised arenes, from one-ring (benzene) to 15-ring (dicoronylene) polycyclic atomatic hydrocarbons (PAHs), and fullerene C 60 , along with theoretical calculations and a systematic analysis of the Cambridge Structural Database. This study establishes C-I⋯π C bonds as directional interactions to arrange planar and curved carbon-only aromatic systems into predictable supramolecular motifs. In >90% of herein presented structures, the C-I⋯π C bonds to PAHs lead to a general ladder motif, in which the arenes act as the rungs and halogen bond donors as the rails, establishing a unique example of a supramolecular synthon based on carbon-only molecules. Besides fundamental importance in the solid-state and supramolecular chemistry of arenes, this synthon enables access to materials with exciting properties based on simple, non-derivatised aromatic systems, as seen from large red and blue shifts in solid-state luminescence and room-temperature phosphorescence upon cocrystallisation., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We explore a series of furan-based non-fullerene acceptors and report their optoelectronic properties, solid-state packing, photodegradation mechanism and application in photovoltaic devices. Incorporating furan building blocks leads to the expected enhanced backbone planarity, reduced band gap and red-shifted absorption of these acceptors. Still, their position in the molecule is critical for stability and device performance. We found that the photodegradation of these acceptors originates from two distinct pathways: electrocyclic photoisomerization and Diels-Alder cycloaddition of singlet oxygen. These mechanisms are of general significance to most non-fullerene acceptors, and the photostability depends strongly on the molecular structure. Placement of furans next to the acceptor termini leads to better photostability, well-balanced hole/electron transport, and significantly improved device performance. Methylfuran as the linker offers the best photostability and power conversion efficiency (>14 %), outperforming all furan-based acceptors reported to date and all indacenodithiophene-based acceptors. Our findings show the possibility of photostable furan-based alternatives to the currently omnipresent thiophene-based photovoltaic materials., (© 2023 Wiley-VCH GmbH.)

Thiele's hydrocarbon was the first synthesized diradicaloid in the search for stable open-shell structures, but it remains sensitive to oxygen and light. We here report the synthesis of Thiele's fluorocarbon (TFC) and its derivatives exhibiting exceptional thermal, oxidative, and photostability. TFCs have remarkable luminescent properties with yellow to NIR fluorescence and up to 100% quantum yields. X-ray crystallography and ESR spectroscopy confirm their closed-shell quinoidal ground state. As expected from their symmetric nonpolar structure, the TFCs' absorption spectra show no solvent effect, but their emission reveals an extraordinarily large Stokes shift which increases with solvent polarity (from 0.9 eV in cyclohexane to 1.5 eV in acetonitrile). We show that this behavior is a result of sudden polarization, leading to a zwitterionic excited state.

Two-dimensional (2D) assemblies of water-soluble block copolymers have been limited by a dearth of systematic studies that relate polymer structure to pathway mechanism and supramolecular morphology. Here, we employ sequence-defined triblock DNA amphiphiles for the supramolecular polymerization of free-standing DNA nanosheets in water. Our systematic modulation of amphiphile sequence shows the alkyl chain core forming a cell membrane-like structure and the distal π-stacking chromophore block folding back to interact with the hydrophilic DNA block on the nanosheet surface. This interaction is crucial to sheet formation, marked by a chiral "signature", and sensitive to DNA sequence, where nanosheets form with a mixed sequence, but not with a homogeneous poly(thymine) sequence. This work opens the possibility of forming well-ordered, bilayer-like assemblies using a single DNA amphiphile for applications in cell sensing, nucleic acid therapeutic delivery and enzyme arrays., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Operational instability of organic field-effect transistors (OFETs) is one of the key limitations for applications of printed electronics. Environmental species, especially oxygen and water, unintentionally introduced in the OFET channel, can act as either dopants or traps for charge carriers, affecting the electrical characteristics and stability of devices. Here, we report that intentional doping of the benchmark p-type semiconducting polymer (DPP-DTT) with 2,4,5,7-tetranitrofluorenone (TeNF) markedly improves the operational and environmental stability of OFETs. Electrical interrogation of DPP-DTT OFETs in various environments and at variable temperatures shows suppression of electron-induced traps and increase of hole mobility in oxygen-rich environment, while the water molecules act as traps for positive charge carrier, reducing the hole mobility and significantly shifting the threshold voltage. Doping of DPP-DTT with TeNF suppresses both effects, resulting in environmentally independent performance and superior long-term stability of unencapsulated devices for up to 4 months in ambient air. Furthermore, the doped OFETs exhibit dramatically reduced hysteresis and bias-stressed current drop. Such improvement of the environmental and operational stabilities is ascribed to the mitigation of traps induced by the injected minority carrier (electrons) and the reduction of the majority carrier (hole) traps in doped polymer films due to enhanced microstructural order.

Recently, photochemistry of Electron Donor-Acceptor (EDA) complexes employing catalytic amounts of electron donors have become of interest as a new methodology in the catalysis field, allowing for decoupling of the electron transfer (ET) from the bond-forming event. However, examples of practical EDA systems in the catalytic regime remain scarce, and their mechanism is not yet well-understood. Herein, we report the discovery of an EDA complex between triarylamines and α-perfluorosulfonylpropiophenone reagents, catalyzing C-H perfluoroalkylation of arenes and heteroarenes under visible light irradiation in pH- and redox-neutral conditions. We elucidate the mechanism of this reaction using a detailed photophysical characterization of the EDA complex, the resulting triarylamine radical cation, and its turnover event., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Integrating plasmonic nanoparticles into the photoactive metal-organic matrix is highly desirable due to the plasmonic near field enhancement, complementary light absorption, and accelerated separation of photogenerated charge carriers at the junction interface. The construction of a well-defined, intimate interface is vital for efficient charge carrier separation, however, it remains a challenge in synthesis. Here we synthesize a junction bearing intimate interface, composed of plasmonic Ag nanoparticles and matrix with silver node via a facile one-step approach. The plasmonic effect of Ag nanoparticles on the matrix is visualized through electron energy loss mapping. Moreover, charge carrier transfer from the plasmonic nanoparticles to the matrix is verified through ultrafast transient absorption spectroscopy and in-situ photoelectron spectroscopy. The system delivers highly efficient visible-light photocatalytic H 2 generation, surpassing most reported metal-organic framework-based photocatalytic systems. This work sheds light on effective electronic and energy bridging between plasmonic nanoparticles and organic semiconductors., (© 2023. The Author(s).)

Organic room-temperature phosphorescence, a spin-forbidden radiative process, has emerged as an interesting but rare phenomenon with multiple potential applications in optoelectronic devices, biosensing and anticounterfeiting. Covalent organic frameworks (COFs) with accessible nanoscale porosity and precisely engineered topology can offer unique benefits in the design of phosphorescent materials, but these are presently unexplored. Here, we report an approach of covalent doping, whereby a COF is synthesized by copolymerization of halogenated and unsubstituted phenyldiboronic acids, allowing for random distribution of functionalized units at varying ratios, yielding highly phosphorescent COFs. Such controlled halogen doping enhances the intersystem crossing while minimizing triplet-triplet annihilation by diluting the phosphors. The rigidity of the COF suppresses vibrational relaxation and allows a high phosphorescence quantum yield (Φ Phos  ≤ 29%) at room temperature. The permanent porosity of the COFs and the combination of the singlet and triplet emitting channels enable a highly efficient COF-based oxygen sensor, with an ultra-wide dynamic detection range (~10 3 -10 -5  torr of partial oxygen pressure)., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Surface-confined reactions represent a powerful approach for the precise synthesis of low-dimensional organic materials. A complete understanding of the pathways of surface reactions would enable the rational synthesis of a wide range of molecules and polymers. Here, we report different reaction pathways of tetrathienylbenzene (T1TB) and its extended congener tetrakis(dithienyl)benzene (T2TB) on Cu(111), investigated using scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. Both T1TB and T2TB undergo desulfurization when deposited on Cu(111) at room temperature. Deposition of T1TB at 453 K yields pentacene through desulfurization, hydrogen transfer, and a cascade of intramolecular cyclization. In contrast, for T2TB the intramolecular cyclization stops at anthracene and the following intermolecular C-C coupling produces a conjugated ladder polymer. We show that tandem desulfurization/C-C coupling provides a versatile approach for growing carbon-based nanostructures on metal surfaces.

Reversible control of molecular self-assembly is omnipresent in adaptive biological systems, yet its realization in artificial systems remains a major challenge. Using scanning tunneling microscopy and density functional theory calculations, we show that a 2D supramolecular network formed by terthienobenzenetricarboxylic acid (TTBTA) can undergo a reversible structural transition between a porous and dense phase in response to different molecular signals (trimethyltripyrazolotriazine (TMTPT) and C 60 ). TMTPT molecules can induce a phase transition from the TTBTA honeycomb to the dense phase, whereas a reverse transition can be triggered by introducing C 60 molecules. This response stems from the selective association between signal molecules and TTBTA polymorphs. The successful realization of reversible molecular transformation represents important progress in controlling supramolecular surface nanostructures and could be potentially applicable in various areas of nanotechnology, including phase control, molecular sensing, and "smart" switchable surfaces.

Despite the importance of the on-surface Ullmann coupling for synthesis of atomically precise carbon nanostructures, it is still unclear whether this reaction is catalyzed by surface atoms or adatoms. Here, the feasibility of the adatom creation and adatom-catalyzed Ullmann coupling of chloro-, bromo-, and iodobenzene on Cu(111), Ag(111), and Au(111) surfaces is examined using density functional theory modeling. The extraction of a metal atom is found to be greatly facilitated by the formation of strong phenyl-metal bonds, making the extraction energy barrier comparable to, and in the case of Ag(111) even lower than, that for the competing surface-catalyzed phenyl-phenyl bond formation. However, if the phenyl-adatom bonds are too strong, as on Cu(111) and Ag(111), they create an insurmountable barrier for the subsequent adatom-catalyzed C-C coupling. In contrast, Au adatoms do not bind phenyl groups strongly and can catalyze the C-C bond formation almost as efficiently as surface atoms.

Herein, we elucidate the photodegradation pathway of A-D-A-type non-fullerene acceptors for organic photovoltaics. Using IT-4F as a benchmark example, we isolated the photoproducts and proved them isomers of IT-4F formed by a 6-e electrocyclic reaction between the dicyanomethylene unit and the thiophene ring, followed by a 1,5-sigmatropic hydride shift. This photoisomerization was accelerated under inert conditions, as explained by DFT calculations predicting a triplet-mediated reaction path (quenchable by oxygen). Adding controlled amounts of the photoproduct P1 to PM6:IT-4F bulk heterojunction cells led to a progressive decrease in photocurrent and fill factor attributed to its poor absorption and charge transport properties. The reaction is a general photodegradation pathway for a series of A-D-A molecules with 1,1-dicyanomethylene-3-indanone termini, and its rate varies with the structure of the donor and acceptor moiety., (© 2021 Wiley-VCH GmbH.)

On-surface Ullmann coupling is an established method for the synthesis of 1D and 2D organic structures. A key limitation to obtaining ordered polymers is the uncertainty in the final structure for coupling via random diffusion of reactants over the substrate, which leads to polymorphism and defects. Here, a topotactic polymerization on Cu(110) in a series of differently-halogenated para-phenylenes is identified, where the self-assembled organometallic (OM) reactants of diiodobenzene couple directly into a single, deterministic product, whereas the other precursors follow a diffusion driven reaction. The topotactic mechanism is the result of the structure of the iodine on Cu(110), which controls the orientation of the OM reactants and intermediates to be the same as the final polymer chains. Temperature-programmed X-ray photoelectron spectroscopy and kinetic modeling reflect the differences in the polymerization regimes, and the effects of the OM chain alignments and halogens are disentangled by Nudged Elastic Band calculations. It is found that the repulsion or attraction between chains and halogens drive the polymerization to be either diffusive or topotactic. These results provide detailed insights into on-surface reaction mechanisms and prove the possibility of harnessing topotactic reactions in surface-confined Ullmann polymerization., (© 2021 Wiley-VCH GmbH.)

Boroxine and dioxaborole are the first and some of the most studied synthons of covalent organic frameworks (COFs). Despite their wide application in the design of functional COFs over the last 15 years, their synthesis still relies on the original Yaghi's condensation of boronic acids (with itself or with polyfunctional catechols), some of which are difficult to prepare, poorly soluble, or unstable in the presence of water. Here, we propose a new synthetic approach to boroxine COFs (on the basis of the transesterification of pinacol aryl boronates (aryl-Bpins) with methyl boronic acid (MBA) and dioxaborole COFs (through the metathesis of pinacol boronates with MBA-protected catechols). The aryl-Bpin and MBA-protected catechols are easy to purify, highly soluble, and bench-stable. Furthermore, the kinetic analysis of the two model reactions reveals high reversibility ( K eq ∼ 1) and facile control over the equilibrium. Unlike the conventional condensation, which forms water as a byproduct, the byproduct of the metathesis (MBA pinacolate) allows for easy kinetic measurements of the COF formation by conventional 1 H NMR. We show the generality of this approach by the synthesis of seven known boroxine/dioxaborole COFs whose crystallinity is better or equal to those reported by conventional condensation. We also apply metathesis polymerization to obtain two new COFs, Py4THB and B2HHTP , whose synthesis was previously precluded by the insolubility and hydrolytic instability, respectively, of the boronic acid precursors.

Organic room temperature phosphorescent (ORTP) compounds have recently emerged as a promising class of emissive materials with a multitude of potential applications. However, the number of building blocks that give rise to efficient ORTP materials is still limited, and the rules for engineering phosphorescent properties in organic solids are not well understood. Here, we report ORTP in a series of N -substituted acridone derivatives with electron-donating, electron-withdrawing, and sterically bulky substituents. X-ray crystallography shows that the solid-state packing varies progressively between coparallel and antiparallel π-stacking and separated π-dimers, depending on the size of the substituent. The detailed photophysical studies supported by DFT calculations reveal complex dynamics of singlet and triplet excited states, depending on the electronic effects of substituents and solid-state packing. The programmable molecular packing provides a lever to control the triplet-triplet annihilation that is manifested as delayed fluorescence in acridone derivatives with continuous (both parallel and antiparallel) π-stacking.

Planarity is essential for many organic electronic materials as it maximizes the intramolecular π-orbital overlap and enables efficient intermolecular interactions through π-stacking. We propose a statistical way of quantifying the planarity of a wide range of conjugated systems. The quantification takes into account all torsional conformations and their relative contribution to the overall structural disorder, through a planarity index ⟨cos 2 ϕ⟩. The propensity for planarization and the effect of rotational disorder were examined for a series of commonly used building blocks. The application of the analysis to extended conjugated systems and the correlations between the gas-phase ⟨cos 2 ϕ⟩ and crystallographically observed planarity in the solid state were explored. Our calculations also reveal a previously unrecognized effect of increasing band gap upon planarization for conjugated systems coupling strong electron donor and acceptor units., (© 2020 Wiley-VCH GmbH.)

Red luminescence is found in off-white tris(iodoperchlorophenyl)methane (3I-PTM H ) crystals which is characterized by a high photoluminescence quantum yield (PLQY 91 %) and color purity (CIE coordinates 0.66, 0.34). The emission originates from the doublet excited state of the neutral radical 3I-PTM R , which is spontaneously formed and becomes embedded in the 3I-PTM H matrix. The radical defect can also be deliberately introduced into 3I-PTM H crystals which maintain a high PLQY with up to 4 % radical concentration. The immobilized iodinated radical demonstrates excellent photostability (estimated half-life >1 year under continuous irradiation) and intriguing luminescent lifetime (69 ns). TD-DFT calculations demonstrate that electron-donating iodine atoms accelerate the radiative transition while the rigid halogen-bonded matrix suppresses the nonradiative decay., (© 2020 Wiley-VCH GmbH.)

Two-dimensional materials with high charge carrier mobility and tunable band gaps have attracted intense research effort for their potential use in nanoelectronics. Two-dimensional π-conjugated polymers constitute a promising subclass because the band structure can be manipulated by varying the molecular building blocks while preserving key features such as Dirac cones and high charge mobility. The major barriers to the application of two-dimensional π-conjugated polymers have been the small domain size and high defect density attained in the syntheses explored so far. Here, we demonstrate the fabrication of mesoscale ordered two-dimensional π-conjugated polymer kagome lattices with semiconducting properties, Dirac cone structures and flat bands on Au(111). This material has been obtained by combining a rigid azatriangulene precursor and a hot dosing approach, which favours molecular diffusion and eliminates voids in the network. These results open opportunities for the synthesis of two-dimensional π-conjugated polymer Dirac cone materials and their integration into devices.

We report a series of highly emissive azatriangulenetrione (TANGO) solids in which the luminescent properties are controlled by engineering the molecular packing by adjusting the steric size of substituents. The co-alignment of "phosphorogenic" carbonyl groups within the π-stacks results in an almost pure triplet emission in HTANGO, TCTANGO, TBTANGO and TITANGO, while their rotation by ≈60° in the sterically hindered tBuTANGO leads to an almost pure singlet emission. Despite strong π-interactions, aggregation-induced quenching and triplet-triplet annihilation are avoided in HTANGO and TCTANGO which display efficient phosphorescence in the solid state. To our knowledge, HTANGO with the solid-state phosphorescence quantum yield of 42 % at room temperature is the most efficient phosphor composed of the 1 st /2 nd raw elements only., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The nitro group (NO2) is one of the most common electron-withdrawing groups but it has rarely been used in the design of organic semiconductors (OSCs). Herein, we report the n-type semiconducting behavior of simple fluorenone derivatives functionalized with NO2 and CN groups. While the electron mobilities measured in the thin film field-effect transistors are modest (10-6-10-4 cm2 V-1 s-1), the nitrofluorenone OSCs offer excellent air-stability and remarkable tunability of energy levels via facile modification of the substitution pattern. We study the effect of substituents on the electrochemical properties, molecular and crystal structure, and the charge transport properties of nitrofluorenones to revitalize the underestimated potential of NO2 functionalization in organic electronics.

We report the first transformation between crystalline vinylene-linked two-dimensional (2D) polymers and crystalline cyclobutane-linked three-dimensional (3D) polymers. Specifically, absorption-edge irradiation of the 2D poly(arylenevinylene) covalent organic frameworks (COFs) results in topological [2 + 2] cycloaddition cross-linking of the π-stacked layers in 3D COFs. The reaction is reversible, and heating to 200 °C leads to a cycloreversion while retaining the COF crystallinity. The resulting difference in connectivity is manifested in the change of mechanical and electronic properties, including exfoliation, blue-shifted UV-vis absorption, altered luminescence, modified band structure, and different acid-doping behavior. The Li-impregnated 2D and 3D COFs show a significant room-temperature ion conductivity of 1.8 × 10 -4 S/cm and 3.5 × 10 -5 S/cm, respectively. Even higher room-temperature proton conductivity of 1.7 × 10 -2 S/cm and 2.2 × 10 -3 S/cm was found for H 2 SO 4 -treated 2D and 3D COFs, respectively.

Stereocontrolled multilayer growth of supramolecular porous networks at the interface between graphite and a solution was investigated. For this study, we designed a chiral dehydrobenzo[12]annulene (DBA) building block bearing alkoxy chains substituted at the 2 position with hydroxy groups, which enable van der Waals stabilization in a layer and potential hydrogen-bonding interactions between the layers. Bias voltage-dependent scanning tunneling microscopy (STM) experiments revealed the diastereospecificity of the bilayer with respect to both the intrinsic chirality of the building blocks and the supramolecular chirality of the self-assembled networks. Top and bottom layers within the same crystalline domain were composed of the same enantiomers but displayed opposite supramolecular chiralities.

Perovskite light-emitting diodes (PeLEDs) exhibit high external quantum efficiencies (EQEs), emerging as a next-generation lighting and display technology. Nevertheless, they suffer from severe efficiency roll-off at high luminance, particularly in the case of blue and green emissions, which is one of the major bottlenecks in their industrial applications. Here, we attack this problem using a rare-earth metal, Yb, as cathode interface layer (CIL) for green PeLEDs. By adopting a new device configuration of ITO/TFB/FA-based quasi-2D perovskite/TPBi/Yb/Ag, we achieved a peak current efficiency (CE) of 22.3 cd/A with a corresponding EQE of 5.28% and a high maximum luminance of 19 160 cd/m 2 . Importantly, the maximum CE of 22.0 cd/A at 2000 cd/m 2 slightly decreased to 16.8 cd/A at 5000 cd/m 2 and maintained a still-decent value of 12.0 cd/A at a high luminance of 10 000 cd/m 2 , exhibiting a remarkably low efficiency roll-off. Our Yb-incorporated devices significantly outperformed the PeLEDs containing conventional CILs, including Mg and Liq, in terms of peak efficiency, efficiency roll-off, and operational lifetime. We attribute this encouraging performance to barrier-free, efficient electron injection enabled by the low work function of Yb (2.6 eV), which led to a high electron current, nearly approaching the hole current in hole-dominant PeLEDs, as confirmed by the single-carrier device measurements. In addition, we also present Yb-incorporated PeLEDs containing Cs-based quasi-2D perovskite as the emissive layer, which displayed an impressive CE of 51.3 cd/A with a corresponding EQE of 16.4% and a maximum luminance of 14 240 cd/m 2 , and still demonstrated a reduced efficiency roll-off comparing to that of the Liq-based equivalent. These results unveil the inspiring prospects of Yb as an efficient CIL for PeLEDs toward high efficiency with curtailed roll-off.

Two-dimensional (2D) nanomaterials, such as graphene and single layer covalent organic frameworks (sCOFs) are being widely studied due to their unusual structure/property relationships. sCOFs typically feature atomic thickness, intrinsic nanoscale porosity and a crystalline lattice. Compared to other organic 2D materials, sCOFs exhibit major advantages including topological designation and constitutional tunability. This review describes the state of the art of surface-confined sCOFs, emphasizing reticular design, synthesis approaches, and key challenges related to improving quality and exploring applications.

We report the serendipitous discovery and synthesis of an indigoid "semi-Nindigo" ( 2 ) via oxidation of a diindolopyrrole ( 1 ). The reaction of 2 with BF 3 Et 2 O affords the borylated derivative ( 3 ). The electronic spectra of 2 and 3 possess intense long wave absorptions near 600 and 650 nm. Compound 3 is weakly emissive in the near-infrared. Thin-film OFETs fabricated with 1 and 2 both exhibited hole mobility of 10 -5 and 10 -3 cm 2 /(V s), respectively.

Surface-confined synthesis is a promising approach to build complex molecular nanostructures including macrocycles. However, despite the recent advances in on-surface macrocyclization under ultrahigh vacuum, selective synthesis of monodisperse and multicomponent macrocycles remains a challenge. Here, we report on an on-surface formation of [6 + 6] Schiff-base macrocycles via dynamic covalent chemistry. The macrocycles form two-dimensional crystalline domains on the micrometer scale, enabled by dynamic conversion of open-chain oligomers into well-defined ∼3.0 nm hexagonal macrocycles. We further show that by tailoring the length of the alkyl substituents, it is possible to control which of three possible products-oligomers, macrocycles, or polymers-will form at the surface. In situ scanning tunneling microscopy imaging combined with density functional theory calculations and molecular dynamics simulations unravel the synergistic effect of surface confinement and solvent in leading to preferential on-surface macrocyclization.

Herein, we report a new molecule structure modification strategy for non-fullerene small-molecule electron acceptors (NFAs) for solar cells through trifluoromethylation of end-capping groups. The synthesized trifluoromethylated acceptor ITCF3 exhibits narrower band gap, stronger light absorption, lower molecular energy levels, and better electron transport property compared to the reference NFA without the trifluoromethyl group (ITIC). Bulk heterojunction solar cells based on ITCF3 combined with the PM6 polymer donor exhibit a significantly improved power conversion efficiency of 13.3% compared with the ITIC-based device (8.4%). This work reveals great potential of trifluoromethylation in the design of efficient photovoltaic acceptor materials.

The black crystalline (aza)triangulene-based covalent organic framework TANG-COF was synthesized from its trinitro-TANG precursor via a one-pot, two-step reaction involving Pd-catalyzed hydrogenation and polycondensation with an aromatic dialdehyde. High crystallinity and permanent porosity of the layered two-dimensional (2D) structure were established. The rigid, electron-rich trioxaazatriangulene (TANG) building block enables strong π-electron interactions manifested in broad absorptions across the visible and NIR regions ( E g ≈ 1.2 eV). The high HOMO energy of TANG-COF (-4.8 eV) enables facile p doping, resulting in electrical conductivity of up to 10 -2 S/cm and room-temperature paramagnetic behavior with a spin concentration of ∼10%. DFT calculations reveal dispersion of the highest occupied band both within the 2D polymer layers (0.28 eV) and along their π-stacked direction (0.95 eV).

The facile synthesis of a series of benzodithiophene (BDT)- and indacenodithiophene (IDT)-based A-D-A oligomers with different end groups is reported, and their properties are studied by optical spectroscopy, electrochemistry, and density functional theory calculations. The permutation of central and terminal units tunes the optoelectronic properties and photovoltaic device characteristics in a predictable way, aiding in the rational design of small molecule semiconducting materials. Among the three rhodanine-derived terminal groups, N -alkylthiazolonethione revealed the strongest electron-withdrawing character, resulting in the lowest band gap, the highest stability, and the best photovoltaic device performance. The crystallographic analysis of two IDT derivatives yielded a highly unusual three-dimensional packing of the conjugated backbone, which is likely responsible for the remarkable photovoltaic performance of such A-D-A semiconductors.

π-Conjugated organic materials possess a wide range of tunable optoelectronic properties which are dictated by their molecular structure and supramolecular arrangement. While many efforts have been put into tuning the molecular structure to achieve the desired properties, rational supramolecular control remains a challenge. Here, we report a novel series of supramolecular materials formed by the co-assembly of weak π-electron donor (indolo[2,3-a]carbazole) and acceptor (aromatic o-quinones) molecules via complementary hydrogen bonding. The resulting polarization creates a drastic perturbation of the molecular energy levels, causing strong charge transfer in the weak donor-acceptor pairs. This leads to a significant lowering (up to 1.5 eV) of the band gaps, intense absorption in the near-IR region, very short π-stacking distances (≥3.15 Å), and strong ESR signals in the co-crystals. By varying the strength of the acceptor, the characteristics of the complexes can be tuned between intrinsic, gate-, or light-induced semiconductivity with a p-type or ambipolar transport mechanism., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The formation of ordered molecular structures on surfaces is determined by the balance between molecule-molecule and molecule-substrate interactions. Whether the aggregation process is guided by non-covalent forces or on-surface reactions, a deeper understanding of these interactions is pivotal to formulating a priori predictions of the final structural features and the development of bottom-up fabrication protocols. Theoretical models of molecular systems corroborate the information gathered through experimental observations and help explain the thermodynamic factors that underpin on-surface phase transitions. Here, we report a scanning tunneling microscopy investigation of a tribromo-substituted heterotriangulene on the Au(111) surface, which initially forms an extended close-packed ordered structure stabilized by BrBr halogen bonds when deposited at room temperature. X-ray photoelectron spectroscopy reveals that annealing the self-assembled layer induces a fraction of the molecular precursors to partially dehalogenate that in turn leads to the formation of a less stable BrO non-covalent network which coexists with the short oligomers. Density functional theory (DFT) and Monte Carlo (MC) simulations illustrate how dimer moieties act as defects whose steric hindrance prevents the retention of the more stable configuration. A small number of dimers is sufficient to drive the molecular reorganization into a lower cohesive energy phase. Our study shows the importance of a combined DFT - MC approach to understand the evolution of molecular systems on substrates.

We report on the synthesis of a covalent organic framework based on the low-symmetry 1,3-benzenediboronic acid precursor. Two distinct polymorphs are obtained, a honeycomb network and Sierpiński triangles, as elucidated by scanning tunneling microscopy. Control over polymorph formation was achieved by varying the precursor concentration for on-surface synthesis.

Designing structural order in electronically active organic solids remains a great challenge in the field of materials chemistry. Now, 2D poly(arylene vinylene)s prepared as highly crystalline covalent organic frameworks (COFs) by base-catalyzed aldol condensation of trimethyltriazine with aromatic dialdehydes are reported. The synthesized polymers are highly emissive (quantum yield of up to 50 %), as commonly observed in their 1D analogues poly(phenylene vinylene)s. The inherent well-defined porosity (surface area ca. 1000 m 2  g -1 , pore diameter ca. 11 Å for the terephthaldehyde derived COF-1) and 2D structure of these COFs also present a new set of properties and are likely responsible for the emission color, which is sensitive to the environment. COF-1 is highly hydrophilic and reveals a dramatic macroscopic structural reorganization that has not been previously observed in framework materials., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report the first π-conjugated macrocyclic system with an oligofuran backbone. The calculated HOMO-LUMO gap is similar to that of the corresponding linear polymer, indicating a remarkable electron delocalization. The X-ray structure reveals a planar conformation, in contrast to the twisted conformation of macrocyclic oligothiophenes. The intermolecular π-π stacking distance is extremely small (3.17 Å), indicating very strong interactions. The macrocycle forms large π-aggregates in solution and shows a tendency toward highly ordered multilayer adsorption at the solid-liquid interface. The face-on orientation of molecules explains the higher hole mobility observed in the out-of-plane direction., (This journal is © The Royal Society of Chemistry 2019.)

We report on mixed ordered monolayers of the electron acceptor-type molecule tetracyano - 2,6 - naphthoquinodimethane (TNAP) and the electron donor-type molecule hexathiapentacene (HTPEN). This investigation was motivated by the general question which type of mixed stoichiometric structures are formed on a surface by molecules that are otherwise typically used for the synthesis of bulk charge-transfer materials. The layers were obtained by vacuum deposition on the Ag(100) surface and analyzed by low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM). The formation of the mixed structure occurs spontaneously. An important motif for the structure formation is given by hydrogen bonds between the TNAP molecules. Both molecules, TNAP and HTPEN also form well-ordered monolayers on the Ag(100) surface on their own. In all structures, the molecules are adsorbed in a planar orientation on the surface. We discuss the influence of intermolecular charge transfer on the ordering in the mixed structure.

Ullmann coupling or, more generally, dehalogenative aryl-aryl coupling, is one of the most widely exploited chemical reactions to obtain one- and two-dimensional polymers on metal surfaces. It is generally described as a two-step reaction: (i) dehalogenation, resulting in the formation of a stable intermediate organometallic phase and subsequent (ii) C-C coupling. The topology of the resulting polymer depends on the number and positions of the halogen atoms in the haloaromatic precursor, although its orientation and order are determined by the structure of the intermediate phase. Hitherto, only one intermediate structure, identified as an organometallic (OM) phase, has been reported for such a reaction. Here we demonstrate the formation of two distinct OM phases during the temperature-induced growth of poly(para-phenylene) from 1,4-dibromobenzene precursors on Cu(110). Beyond the already known linear-OM chains, we show that a phase reorganization to a chessboard-like 2D-OM can be activated in a well-defined temperature range. This new intermediate phase, revealed only when the reaction is carried out at low molecular coverages, was characterized by X-ray photoelectron spectroscopy, scanning tunneling microscopy and near-edge X-ray absorption fine structure spectroscopy, and modeled by density functional theory calculations. Our data show that the 2D-OM remains stable after cooling down the sample and is stabilized by four-Cu clusters at each node. The observation of such unexpected intermediate phase shows the complexity of the mechanisms underlying on-surface synthesis and broadens the understanding of Ullmann coupling, which continues to be astonishing despite its extensive use.

Ullmann coupling of halogenated aromatics is widely used in on-surface synthesis of two-dimensional (2D) polymers and graphene nanoribbons. It stands out among other reactions for regioselectively connecting aromatic monomers into 1D and 2D π-conjugated polymers, whose final structure and properties are determined by the initial building blocks. Thanks to their exceptional electronic properties, thiophene-containing monomers are frequently used for the synthesis of various conjugated materials. On the other hand, their use in on-surface polymerization is hampered by the possibility of ring opening when adsorbed on metal surfaces. In the present work, we mapped the temperature regime for these two competing reactions by investigating the adsorption of a thiophene-based prochiral molecule using scanning tunneling microscopy, X-ray photoelectron spectroscopy and density functional theory calculations. We followed the formation of organometallic (OM) networks, their evolution into covalent structures and the competition between C-C coupling and thiophene ring opening. The effect of surface reactivity was explored by comparing the adsorption on three (111) coinage metal substrates, namely Au, Ag and Cu. While outlining strategies to minimize the ring opening reaction, we found that the surface temperature during deposition is of paramount importance for the preparation of 2D OM networks, greatly enhancing the overall ordering of the product by depositing on hot Ag surface. Notably, the same protocol permits the creation of OM structures on the air-stable Au surface, thereby allowing the synthesis and application of 2D OM networks outside the ultra-high vacuum environment.

Understanding how molecules interact to form large-scale hierarchical structures on surfaces holds promise for building designer nanoscale constructs with defined chemical and physical properties. Here, we describe early advances in this field and highlight upcoming opportunities and challenges. Both direct intermolecular interactions and those that are mediated by coordinated metal centers or substrates are discussed. These interactions can be additive, but they can also interfere with each other, leading to new assemblies in which electrical potentials vary at distances much larger than those of typical chemical interactions. Earlier spectroscopic and surface measurements have provided partial information on such interfacial effects. In the interim, scanning probe microscopies have assumed defining roles in the field of molecular organization on surfaces, delivering deeper understanding of interactions, structures, and local potentials. Self-assembly is a key strategy to form extended structures on surfaces, advancing nanolithography into the chemical dimension and providing simultaneous control at multiple scales. In parallel, the emergence of graphene and the resulting impetus to explore 2D materials have broadened the field, as surface-confined reactions of molecular building blocks provide access to such materials as 2D polymers and graphene nanoribbons. In this Review, we describe recent advances and point out promising directions that will lead to even greater and more robust capabilities to exploit designer surfaces.