Bidirectional Phase Transformation of Supramolecular Networks Using Two Molecular Signals.

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). 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 molecules.

Adatoms in the Surface-Confined Ullmann Coupling of Phenyl Groups.

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.

Mechanism of the Photodegradation of A-D-A Acceptors for Organic Photovoltaics*.

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).

Identification of Topotactic Surface-Confined Ullmann-Polymerization.

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.

Synthesis of Boroxine and Dioxaborole Covalent Organic Frameworks via Transesterification and Metathesis of Pinacol Boronates.

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).

Room Temperature Phosphorescence vs Triplet-Triplet Annihilation in N-Substituted Acridone Solids.

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 -substituted acridone derivatives with electron-donating, electron-withdrawing, and sterically bulky substituents.

Quantifying Planarity in the Design of Organic Electronic Materials.

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 ϕ⟩.

A Pure-Red Doublet Emission with 90 % Quantum Yield: Stable, Colorless, Iodinated Triphenylmethane Solid.

Red luminescence is found in off-white tris(iodoperchlorophenyl)methane (3I-PTM ) crystals which is characterized by a high photoluminescence quantum yield (PLQY 91 %) and color purity (CIE coordinates 0.66, 0.34).

Nitroaromatics as n-type organic semiconductors for field effect transistors.

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.

Transformation between 2D and 3D Covalent Organic Frameworks via Reversible [2 + 2] Cycloaddition.

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.

Stereospecific Epitaxial Growth of Bilayered Porous Molecular Networks.

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.

Boosting Efficiency and Curtailing the Efficiency Roll-Off in Green Perovskite Light-Emitting Diodes via Incorporating Ytterbium as Cathode Interface Layer.

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.

Serendipitous Formation of Semiconducting Semi-Nindigo Indigoid by the Degradation of Diindolopyrrole.

We report the serendipitous discovery and synthesis of an indigoid "semi-Nindigo" () via oxidation of a diindolopyrrole (). The reaction of with BFEtO affords the borylated derivative (). The electronic spectra of and possess intense long wave absorptions near 600 and 650 nm.

Surface-confined single-layer covalent organic frameworks: design, synthesis and application.

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.

Trifluoromethyl Group-Modified Non-Fullerene Acceptor toward Improved Power Conversion Efficiency over 13% in Polymer Solar Cells.

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.

Surface-Confined Macrocyclization Dynamic Covalent Chemistry.

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 dynamic covalent chemistry.

A macrocyclic oligofuran: synthesis, solid state structure and electronic properties.

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.

A Two-Dimensional Poly(azatriangulene) Covalent Organic Framework with Semiconducting and Paramagnetic States.

The black crystalline (aza)triangulene-based covalent organic framework 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 ( ≈ 1.

Crystal Engineering of Room Temperature Phosphorescence in Organic Solids.

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.

Covalent organic frameworks from a monomer with reduced symmetry: polymorphism and Sierpiński triangles.

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.

Strong Enhancement of π-Electron Donor/Acceptor Ability by Complementary DD/AA Hydrogen Bonding.

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.

Understanding the Photovoltaic Behavior of A-D-A Molecular Semiconductors through a Permutation of End Groups.

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, -alkylthiazolonethione revealed the strongest electron-withdrawing character, resulting in the lowest band gap, the highest stability, and the best photovoltaic device performance.

2D Poly(arylene vinylene) Covalent Organic Frameworks via Aldol Condensation of Trimethyltriazine.

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.

Pure and mixed ordered monolayers of tetracyano-2,6-naphthoquinodimethane and hexathiapentacene on the Ag(100) surface.

We report on mixed ordered monolayers of the electron acceptor-type molecule tetracyano2,6naphthoquinodimethane (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).

An unexpected organometallic intermediate in surface-confined Ullmann coupling.

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.