Monodisperse N‐Doped Graphene Nanoribbons Reaching 7.7 Nanometers in Length

The properties of graphene nanoribbons are highly dependent on structural variables such as width, length, edge structure, and heteroatom doping. Therefore, atomic precision over all these variables is necessary for establishing their fundamental properties and exploring their potential applications. An iterative approach is presented that assembles a small and carefully designed molecular building block into monodisperse N-doped graphene nanoribbons with different lengths. To showcase this approach, the synthesis and characterisation of a series of nanoribbons constituted of 10, 20 and 30 conjugated linearly-fused rings (2.9, 5.3, and 7.7 nm in length, respectively) is presented.We are grateful to the Basque Science Foundation for Science (Ikerbasque), POLYMAT, the University of the Basque Country (SGIker), the Deutsche Forschungsgemeinschaft (MA 5215/4-1), Gobierno de Espana (Ministerio de Economia y Competitividad CTQ2016-77970-R and CTQ2015-71936-REDT), Gobierno Vasco (BERC program and PC2015-1-01(0637)), Diputacion Foral de Guipuzcoa (OF215/2016(ES)), CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT ref. UID/CTM/50011/2013), ON2 (NORTE-07-0162-FEDER-000086), and the FP7 framework program of the European Union (ERA Chemistry, Marie Curie Career Integration Grant No. 618247 (NIRVANA)). This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 664878. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement no. 722951)

A Wavy Two-Dimensional Covalent Organic Framework from Core-Twisted Polycyclic Aromatic Hydrocarbons

A high degree of crystallinity is an essential aspect in two-dimensional covalent organic frameworks, as many properties depend strongly on the structural arrangement of the different layers and their constituents. We introduce herein a new design strategy based on core-twisted polycyclic aromatic hydrocarbon as rigid nodes that give rise to a two-dimensional covalent organic framework with a wavy honeycomb (chairlike) lattice. The concave–convex self-complementarity of the wavy two-dimensional lattice guides the stacking of framework layers into a highly stable and ordered covalent organic framework that allows a full 3D analysis by transmission electron microscopy revealing its chairlike honeycomb facets and aligned mesoporous channels. Remarkably, the waviness of the framework does not disrupt the interlayer π–π stacking that shows charge transporting properties similar to those of planar covalent organic frameworks. The implementation of core-twisted aromatics as building blocks for covalent organic frameworks brings new possibilities in the design of highly ordered organic materials

Accuracy of dispersion interactions in semiempirical and molecular mechanics models : the benzene dimer case

The benzene dimer is arguably the simplest molecular analogue of graphitic materials. We present the systematic study of minima and transition states of the benzene dimer with semiempirical and molecular mechanics (MM) methods. Full minimizations on all conformations were performed and the results, geometries, and binding energies were compared with CCSD(T) and DFT-D results. MM yields the best results with three force fields MM3, OPLS, and AMOEBA, which reproduced nine out of the ten stationary points of the benzene dimer. We obtained new parameters for MM3 and OPLS that successfully reproduce all structures of the benzene dimer and showed improved accuracy over DFT-D in most dimer geometries. Semiempirical models were, unexpectedly, less accurate than MM methods. The most accurate semiempirical method for the benzene dimer is PM6-DH2. DFT-D was the only Hamiltonian that reproduced the variations of energy with geometry from CCSD(T) calculations accurately and is the method of choice for energies of periodic and molecular calculations of graphitic systems. In contrast, MM represents an accurate alternative to calculate geometries.Fundação para a Ciência e a Tecnologia (FCT)Financial support from Fundação para a Ciência e Tecnologia doctoral grant no. SFRH/BD/61894/2009, REQUIMTE PEst- C/EQB/LA0006/2011, the program Ciência 2008 and contracts PEst-OE/EEI/UI0752/2014 and CONC-REEQ/ 443/2005 are gracefully acknowledged

Tailoring supercontinuum generation beyond 2 μm in step-index tellurite fibers

We report numerical and experimental demonstrations of flexible group-velocity dispersion regimes in step-index tellurite fibers by fine control of the fiber core diameter. Our simple fiber design allowed us to explore various nonlinear propagation regimes beyond 2 μm, which involved careful control of four-wave mixing processes. Combined with the recent development of 2 μm fiber lasers, we present an easy way to tailor supercontinuum generation and related coherence features in the high-demand 1.5–3.5 μm spectral regio

Twisted Aromatic Frameworks: Readily Exfoliable and Solution-Processable Two-Dimensional Conjugated Microporous Polymers

Twisted two-dimensional aromatic frameworks have been prepared by overcrowding the nodes with bulky and rigid substituents. The highly distorted aromatic framework with alternating out-of-plane substituents results in diminished interlayer interactions that favor the exfoliation and dispersion of individual layers in organic media.status: publishe

A partially-planarised hole-transporting quart-p-phenylene for perovskite solar cells

Herein, we describe the synthesis of a hole transporting material based on a partially planarised quart-p-phenylene core incorporating tetraketal and diphenylamine substituents that show optimal energy levels and solubility for perovskite solar cell applications. The triple-cation perovskite devices incorporating such quart-p-phenylene derivatives show power-conversion efficiencies, short circuit currents, open circuit voltages, and fill factors that are comparable to those of spiro-OMeTAD