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Two-dimensional (2D) covalent organic frameworks (COFs) are an emerging class of promising 2D materials with high crystallinity and tunable structures. However, the low electrical conductivity impedes their applications in electronics and optoelectronics. Integrating large π-conjugated building blocks into 2D lattices to enhance efficient π-stacking and chemical doping is an effective way to improve the conductivity of 2D COFs. Herein, two nonplanar 2D COFs with kagome (DHP-COF) and rhombus (

Organic cages have gained increasing attention in recent years as molecular hosts and porous materials. Among these, barrel-shaped cages or molecular nanobarrels are promising systems to encapsulate large hosts as they possess windows of the same size as their internal cavity. However, these systems have received little attention and remain practically unexplored despite their potential. Herein, we report the design and synthesis of a new trigonal prismatic organic nanobarrel with two large triangular windows with a diameter of 12.7 Å optimal for the encapsulation of C60. Remarkably, this organic nanobarrel shows a high affinity for C60 in solvents in which C60 is virtually insoluble, providing stable solutions of C60.

Herein, we show that twisted molecular nanoribbons with as many as 322 atoms in the aromatic core are efficient gelators capable of self-assembling into ordered pi-gels with morphologies and sol-gel transitions that vary with the length of the nanoribbon. In addition, the nanoribbon gels show a red fluorescence and also pseudoconductivity values in the same range as current state-of-the-art pi-gels. This work was carried out with support from the Basque Science Foundation for Science (Ikerbasque), POLYMAT, the University of the Basque Country, Diputacion de Guipuzcoa, Gobierno Vasco (PIBA_2022_1_0031 and BERC programme) and Gobierno de Espana (Projects PID2021-124484OB-I00 and CEX2020-001067-M financed by MCIN/AEI/10.13039/501100011033). Project (PCI2022-132921) funded by the Agencia Estatal de Investigacion through the PCI 2022 and M-ERA.NET 2021 calls. Technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF) is acknowledged. 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). This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No. 899895. This work was funded by the European Union under the Horizon Europe grant 101046231.

[EN] Molecular nanoribbons are a class of atomically-precise nanomaterials for a broad range of applications. An iterative approach that allows doubling the length of the longest pyrene-pyrazinoquinoxaline molecular nanoribbons is described. The largest nanoribbon obtained through this approach-with a 60 linearly-fused ring backbone (14.9 nm) and a 324-atoms core (C276N48)-shows an extremely high molar absorptivity (values up to 1 198 074 M-1 cm(-1)) that also endows it with a high molar fluorescence brightness (8700 M-1 cm(-1)). This work was carried out with support from the Basque Science Foundation for Science (Ikerbasque), POLYMAT, the University of the Basque Country, Diputacion de Guipuzcoa, Gobierno Vasco (BERC programme) and Gobierno de Espana (Project CEX2020-001067-M financed by MCIN/AEI/10.13039/501100011033). Technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF) is acknowledged. 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). This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No. 899895. In addition, support through the project IF/00894/2015, the advanced computing project CPCA/A2/2524/2020 granting access to the Navigator cluster at LCA-UC and within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020 funded by national funds through the Portuguese Foundation for Science and Technology I.P./MCTES is gratefully acknowledged.

Understanding charge transport in 2D covalent organic frameworks is crucial to increase their performance. Herein a new wavy 2D covalent organic framework has been designed, synthesized and studied to shine light on the structural factors that dominate charge transport.

The quality of crystalline two-dimensional (2D) polymers1-6 is intimately related to the elusive polymerization and crystallization processes. Understanding the mechanism of such processes at the (sub)molecular level is crucial to improve predictive synthesis and to tailor material properties for applications in catalysis7-10 and (opto)electronics11,12, among others13-18. We characterize a model boroxine 2D dynamic covalent polymer, by using in situ scanning tunnelling microscopy, to unveil both qualitative and quantitative details of the nucleation-elongation processes in real time and under ambient conditions. Sequential data analysis enables observation of the amorphous-to-crystalline transition, the time-dependent evolution of nuclei, the existence of 'non-classical' crystallization pathways and, importantly, the experimental determination of essential crystallization parameters with excellent accuracy, including critical nucleus size, nucleation rate and growth rate. The experimental data have been further rationalized by atomistic computer models, which, taken together, provide a detailed picture of the dynamic on-surface polymerization process. Furthermore, we show how 2D crystal growth can be affected by abnormal grain growth. This finding provides support for the use of abnormal grain growth (a typical phenomenon in metallic and ceramic systems) to convert a polycrystalline structure into a single crystal in organic and 2D material systems. ispartof: NATURE vol:603 issue:7903 pages:835-+ ispartof: location:England status: published

[EN]Two-dimensional fused aromatic networks (2D FANs) have emerged as a highly versatile alternative to holey graphene. The synthesis of 2D FANs with increasingly larger lattice dimensions will enable new application perspectives. However, the synthesis of larger analogues is mostly limited by lack of appropriate monomers and methods. Herein, we describe the synthesis, characterisation and properties of an expanded 2D FAN with 90-ring hexagons, which exceed the largest 2D FAN lattices reported to date. This work was carried out with support from the Basque Science Foundation for Science (Ikerbasque),POLYMAT, the University of the Basque Country,Gobierno Vasco (BERC programme) and Gobierno de España (Ministerio de Economía y Competitividad CTQ2016-77970-R).This work was performed under the Maria de Maeztu Units of Excellence Programme–Grant No.CEX-2019-000919-M Ministry of Science, nnovation and Universities.Technica land human support provided by SGIker of UPV/EHU and European funding (ERDFand ESF) is acknowledged.This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (GrantAgreementsNo.722951andNo.714122).This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreements No.664878 and No.899895. In addition,support through the project IF/00894/2015,the advanced computing project CPCA/A2/2524/2020 granting access to the Navigator cluster at LCA-UC and within the scope of the project CICECO-Aveiro Institute of Materials,UIDB/50011/2020&UIDP/50011/2020 funded by national fund sthrough thePortuguese Foundation for Science andTechnologyI. P./MCTES is gratefully acknowl-edged.The Nanoscale & Microscale Research Centre (nmRC), University of Nottingham,is acknowledged fore nabling access to electron microscopy facilities.

[EN] Molecular conformation has an important role in chemistry and materials science. Molecular nanoribbons can adopt chiral twisted helical conformations. However, the synthesis of single-handed helically twisted molecular nanoribbons still represents a considerable challenge. Herein, we describe an asymmetric approach to induce single-handed helicity with an excellent degree of conformational discrimination. The chiral induction is the result of the chiral strain generated by fusing two oversized chiral rings and of the propagation of that strain along the nanoribbon's backbone. This work was carried out with support from the Basque Science Foundation for Science (Ikerbasque), POLYMAT, the University of the Basque Country, Gobierno Vasco (BERC Programme) and Gobierno de Espana (Ministerio de Ciencia e Innovacion, Plan Estatal de Investigacion Cientifica y Tecnica y de Innovacion). Technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF) is acknowledged. 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). This project has received funding from the European Union's Horizon 2020 research and innovation programme under Grant Agreement No. 899895. In addition, support through the project IF/00894/2015, the advanced computing project CPCA/A2/2524/2020 granting access to the Navigator cluster at LCA-UC and within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 and UIDP/50011/2020 funded by national funds through the Portuguese Foundation for Science and Technology I.P./MCTES is gratefully acknowledged.

Chiral materials are an ideal playground for exploring the relation between symmetry, relativistic effects and electronic transport. For instance, chiral organic molecules have been intensively studied to electrically generate spin-polarized currents in the last decade, but their poor electronic conductivity limits their potential for applications. Conversely, chiral inorganic materials such as tellurium have excellent electrical conductivity, but their potential for enabling the electrical control of spin polarization in devices remains unclear. Here, we demonstrate the all-electrical generation, manipulation and detection of spin polarization in chiral single-crystalline tellurium nanowires. By recording a large (up to 7%) and chirality-dependent unidirectional magnetoresistance, we show that the orientation of the electrically generated spin polarization is determined by the nanowire handedness and uniquely follows the current direction, while its magnitude can be manipulated by an electrostatic gate. Our results pave the way for the development of magnet-free chirality-based spintronic devices., This work is supported by the Spanish Ministerio de Ciencia e Innovación (MICINN) under projects RTI2018-094861-B-100 and PID2019-108153GA-I00 and under the Maria de Maeztu Units of Excellence Programme (MDM-2016-0618); by the European Union Horizon 2020 under the Marie Slodowska-Curie Actions (0766025-QuESTech and 892983-SPECTER); and by Intel Corporation under ‘FEINMAN’ and ‘VALLEYTRONICS’ Intel Science Technology Centers. B.M.-G. acknowledges support from the Gipuzkoa Council (Spain) in the frame of the Gipuzkoa Fellows Program. M.S.-R. acknowledges support from La Caixa Foundation (no. 100010434) with code LCF/BQ/DR21/11880030. M.G. acknowledges support from La Caixa Foundation (no. 100010434) for a Junior Leader fellowship (grant no. LCF/BQ/PI19/11690017). A.J. acknowledges support from CRC/TRR 227 of Deutsche Forschungsgemeinschaft.

The key electronic properties of a family of 2D frameworks structurally convergent with holey graphenes were studied. The bandgap of these materials decreases monotonically with size, showing a common trend with anthracenes and kekulenes. This was rationalized by Clar's sextet rule, which reveals a direct relationship between the molecular systems and the 2D frameworks. In addition, a detailed benchmark against experimental data showcased the high quality of the models, which reproduce accurately available electronic properties. Overall, it was shown that DFT can be used to screen and understand the intrinsic bandgaps and electrochemistry potentials for technological applications prior to the synthesis of π-conjugated porous materials. published

Synthetic two-dimensional polymers (2DPs) obtained from well-defined monomers via bottom-up fabrication strategies are promising materials that can extend the realm of inorganic 2D materials. The on-surface synthesis of such 2DPs is particularly popular, however the pathway complexity in the growth of such films formed on solid surfaces is poorly understood. In this contribution, we present a straightforward experimental protocol which allows the synthesis of large-area, defect-free 2DPs based on boroxine linkages at room temperature. We focus on unravelling the multiple pathways available to the polymerizing system for the spatial extension of the covalent bonds. Besides the anticipated 2DP, the system can evolve into self-assembled monolayers of partially fused monodisperse reaction products that are difficult to isolate by conventional synthetic methods or remain in the monomeric state. The access to each pathway can be controlled via monomer concentration and the choice of the solvent. Most importantly, the unpolymerized systems do not evolve into the corresponding 2DP upon annealing, indicating the presence of strong kinetic traps. Using high-resolution scanning tunneling microscopy, we show reversibility in the polymerization process where the attachment and the detachment of monomers to 2DP crystallites could be monitored as a function of time. Finally, we show that the way the 2DP grows depends on the choice of the solvent. Using UV-vis absorption and emission spectroscopy, we reveal that the dominant pathway for 2DP growth is via in-plane self-condensation of the monomers, whereas in the case of an aprotic solvent, the favored growth mode is via π stacking of the monomers. ispartof: ACS NANO vol:14 issue:2 pages:2354-2365 ispartof: location:United States status: published

Singlet fission has emerged as a promising strategy to avoid the loss of extra energy through thermalization in solar cells. A family of dimers consisting of nitrogen‐doped pyrene‐fused acenes that undergo singlet fission with triplet quantum yields as high as 125 % are presented. They provide new perspectives for nitrogenated polycyclic aromatic hydrocarbons and for the design of new materials for singlet fission., Come Together: By introducing dibenzodiazahexacene moieties in a dimeric architecture, a new type of singlet fission material was obtained. Solvent‐dependent triplet quantum yields of up to 125 % were achieved.

Understanding the structural and magnetic properties in layered hybrid organic-inorganic metal halide perovskites (HOIPs) is key for their design and integration in spin-electronic devices. Here, a systematic study is conducted on ten compounds to understand the effect of the transition metal (Cu2+, Mn2+, Co2+), organic spacer (alkyl- and aryl-ammonium), and perovskite phase (Ruddlesden-Popper and Dion-Jacobson) on the properties of these materials. Temperature-dependent Raman measurements show that the crystals’ structural phase transitions are triggered by the motional freedom of the organic cations as well as by the flexibility of the inorganic metal-halide lattice. In the case of Cu2+ HOIPs, an increase of the in-plane anisotropy and a reduction of the octahedra interlayer distance is found to change the behavior of the HOIP from that of a 2D ferromagnet to that of a quasi-3D antiferromagnet. Mn2+ HOIPs show inherent antiferromagnetic octahedra intralayer interactions and a phenomenologically rich magnetism, presenting spin-canting, spin-flop transitions, and metamagnetism controlled by the crystal anisotropy. Co2+ crystals with non-linked tetrahedra show a dominant paramagnetic behavior irrespective of the organic spacer and the perovskite phase. This study demonstrates that the chemical flexibility of HOIPs can be exploited to develop novel layered magnetic materials with tailored magnetic properties., This work was supported by the Spanish MCIN/AEI under Projects PID2019-108153GA-I00, RTI2018-094861-B-I00, PID2021-128004NB-C21, and under the María de Maeztu Units of Excellence Programme (Grant CEX2020-001038-M & CEX2020-001067-M). This work was also supported by the FLAG-ERA grant MULTISPIN, by the Spanish MCIN/AEI with grant number PCI2021-122038-2A. This project received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant Agreement No. 722951). Additionally, this work was carried out with support from the Basque Science Foundation for Science (IKERBASQUE), POLYMAT, EHU/UPV, Gipuzkoa Council, and Basque Government (BERC program). Technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF) is also acknowledged. B.M-G. thanks Gipuzkoa Council (Spain) in the frame of Gipuzkoa Fellows Program. M.G. acknowledges support from la Caixa Foundation (ID 0010434) for a Junior Leader fellowship (Grant No. LCF/BQ/PI19/11690017).

The synthesis of three molecular nanoribbons with a twisted aromatic framework is described. The largest one shows a 53 linearly-fused rings backbone (12.9 nm) and 322 conjugated atoms in its aromatic core (C296N24S2). This new family of nanorib- bons show extremely high molar absorptivities, reaching 986100 M‒1cm‒1, and red-emitting properties.

Synthesis of covalent organic frameworks (COFs) is well-advanced but understanding their nanoscale structure and interaction with other materials remains a significant challenge. Here, we have developed a methodology for the detailed imaging and analysis of COF crystallites using carbon nanotube substrates for COF characterisation. Detailed investigation using powder X-ray diffraction, infrared spectroscopy, mass spectrometry and scanning electron microscopy in conjunction with a local probe method, transmission electron microscopy (TEM), revealed details of COF growth and nucleation at the nanoscale. A boronate ester COF undergoes preferential growth in thea–bcrystallographic plane under solvothermal conditions. Carbon nanotubes were found to not impact the mode of COF growth, but the crystallites on nanotubes were smaller than COF crystallites not on supports. COF crystalline regions with sizes of tens of nanometres exhibited preferred orientation on nanotube surfaces, where thec-axis is oriented between 50 and 90° relative to the carbon surface. The COF/nanotube hybrid structure was found to be more complex than the previously suggested concentric core–shell model and can be better described as a nanocrystalline scaly COF/nanotube hybrid.

Three-dimensional covalent organic frameworks (3D COFs) with a pcu topology have been obtained from distorted polycyclic aromatic hydrocarbons acting as triangular antiprismatic (D3d ) nodes. Such 3D COFs are six-fold interpenetrated as the result of interframework π-stacking, which enable charge transport properties that are not expected for 3D COFs.

Herein, we report the synthesis of mechanically interlocked nitrogenated nanographenes. These systems have been obtained by clipping different tetralactam macrocycles around a 1.9 nm dumbbell-shaped nitrogenated nanographene. Thermal, optoelectronic, and electrochemical characterization of the different mechanically interlocked nanographenes evidence enhanced thermal and photochemical stability, and also absorption and emission properties that vary with the structure of the macrocycle.

In this contribution, we focused on integrating a phenylene-bridged dibenzodiazahexacene dimer (o-DAD), which is singlet fission (SF) active, onto single-walled carbon nanotubes (SWCNTs) as a low-energy sink for energetically low lying excited states that stem from SF. Spectroscopic and microscopic assays assisted in documenting that SWCNT/o-DAD feature high stability in THF as a result of electronic interactions between the individual constituents. For example, statistical Raman analysis underlined n-doping of SWCNTs in the presence of o-DAD. Fluorescence spectroscopy prompted an energy transfer between the individual constituents, a conclusion that was exclusively derived from the quenching of the o-DAD-centered fluorescence. Excitation spectroscopy with a focus on the SWCNT fluorescence confirmed independently this conclusion by showing o-DAD-centered features. Our work was rounded off by time-resolved transient absorption measurements with SWCNT/o-DAD, in which evidence was gathered for the sequential o-DAD-centered SF with an efficiency of 112% followed by a unidirectional energy transfer from o-DAD to SWCNT and a rapid deactivation. The energy transfer efficiency from SF products such as (S1S0)CT and 1(T1T1) exceeded the 100% threshold with values of 115%, which is conventionally found in energy transfer schemes.

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.

The in situ on-surface conversion process from boroxine-linked covalent organic frameworks (COFs) to boronate ester-linked COFs is triggered and catalyzed at room temperature by an electric field and monitored with scanning tunneling microscopy (STM). The adaptive behavior within the generated dynamic covalent libraries (DCLs) was revealed, providing in-depth understanding of the dynamic network switching process. ispartof: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol:142 issue:13 pages:5964-5968 ispartof: location:United States status: published

We use pyrene-4,5,9,10-tetraketone molecules with substituents of varying bulkiness in the 2,7 positions to probe the generality and versatility of the previously reported on-surface coordination of two diketones with a single metal atom, leading to one-dimensional coordination polymers. Three different low index surfaces of group 11 metals (Cu, Ag and Au) are used to provide both the support and the metal atoms for metal-organic coordination. By real space visualisation with single molecule resolution employing scanning tunnelling microscopy we investigate the molecular self-assembly and show how this can be substantiated with the formation of metal-organic linear and cyclic oligomers, depending on the employed substrate.

This microreview covers the different synthetic strategies used to prepare pyrene-fused twistacenes.

An approach for the synthesis of pyrene-fused acenes that allows the introduction of electron-withdrawing cyano groups in key positions that simultaneously (i) induce twists in the aromatic framework and (ii) stabilize the LUMO level is reported. This combination of steric and electronic features provide a twisted, stable, and n-type tetrabenzoheptacene as confirmed by a combination of theoretical calculations and optical, electrochemical, thermal, and electrical characterization.

The on-surface synthesis of atomically flat N-doped graphene on oxidized copper is presented. Besides circumventing the almost standard use of metallic substrates for growth, this method allows producing graphene with similar to 2.0 at % N in a substitutional configuration directly decoupled from the substrate. Angle-resolved photoemission shows a linear energy-momentum dispersion where the Dirac point lies at the Fermi level. Additionally, the N functional centers can be selectively tailored in sp(2) substitutional configuration by making use of a purpose-made molecular precursor: dicyanopyrazophenanthroline (C16H6N6). P.A. acknowledges the contribution of the CA COST Action no. CA15107 (MultiComp). M.C. and A.M.-A. acknowledge support of the Basque Science Foundation for Science (Ikerbasque), POLYMAT, the University of the Basque Country (Grupo de Investigacion GIU17/054 and SGIker), Gobierno Vasco (BERC program), and Gobierno de Espana (Ministerio de Economia y Competitividad CTQ2016-77970R). M.C. and A.M.-A. thank technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF). A.M.-A. acknowledges that 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).

Supramolecular polymers have a lot of potential in the development of new materials because of their inherent recyclability and their self-healing and stimuli-responsive properties. Supramolecular conductive polymers are generally obtained by the assembly of individual disk-like π-conjugated molecules into columnar arrays that provide an optimal channel for electronic transport. We report a new approach to prepare supramolecular polymers by hooking together sigmoidal monomers into 1D arrays of π-stacked anthracene and acridine units, which give rise to micrometer-sized fibrils that show pseudoconductivities in line with other conducting materials. This approach paves the way for the design of new supramolecular polymers constituted by acene derivatives with enhanced excitonic and electronic transporting properties.

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., {"references":["J. Am. Chem. Soc. 2019, 141, 36, 14403–14410"]}

Controlled nitrogen-doping is a powerful methodology to modify the properties of carbon nanostructures and produce functional materials for electrocatalysis, energy conversion and storage, and sensing, among others. Herein, we report a wall- and hybridisation-selective synthetic methodology to produce double-walled carbon nanotubes with an inner tube doped exclusively with graphitic sp2-nitrogen atoms. Our measurements shed light on the fundamental properties of nitrogen-doped nanocarbons opening the door for developing their potential applications.

The synthesis and characterisation of two pyrene-fused phenazinothiadiazole derivatives with different substituents is described. Light-emitting diodes incorporating such derivatives display red to near-infrared electroluminescence with emission peaks at wavelengths as long as 721 nm, illustrating that pyrene-fused bisphenazinothiadiazoles can serve as deep red and NIR emitters.

The synthesis and optical, electrochemical, thermal and electrical characterization of a new and unexpected 1-n-octyloxyperopyrene is reported. The structure of 1-n- octyloxyperopyrene has been unambiguously established by single crystal X-ray diffraction. The solubility of this polycyclic aromatic hydrocarbon, endowed by the alkoxy substituent, allows the fabrication of thin film field-effect transistors by liquid deposition methods. These devices show hole mobilities up to 1.61 × 10–3 cm2 V–1 s–1.

The integrated analytical approach developed in this study offers a powerful methodology for the structural characterisation of complex molecular nanomaterials. Structures of a covalent organic framework based on boronate esters (COF-5) and a conjugated microporous polymer (Aza-CMP) have been investigated by a combination of several electron microscopy techniques elucidating the three-dimensional topology of the complex polycrystalline (COF) and non-crystalline (CMP) materials. Unexpected, aperiodic mesoporous channels of 20-50 nm in diameter were found to be penetrating the COF and CMP particles, which cannot be detected by X-ray diffraction techniques. The mesopores appear to be stable under a range of different conditions and accessible to gas molecules, exhibiting a particular bonding capability with CO2 in the case of the CMP. The mesoporosity is unrelated to the intrinsic chemical structures of the COF or CMP but rather it reflects the mechanisms of polymer particle formation in a polycondensation reaction. The mesopores may be templated by clusters of solvent molecules during the COF or CMP synthesis, leaving cavities within the polymer particles. The unexpected mesoporosity discovered in COF and CMP materials begs for re-assessment of the nature of framework materials and may open new opportunities for applications of these molecular materials in gas sorption or catalysis. We acknowledge the support of the Engineering and Physical Science Research Council (EPSRC) for funding, and the Nanoscale and Microscale Research Centre (nmRC) for access to instrumentation. We are also grateful to the Basque Science Foundation for Science (Ikerbasque), POLYMAT, the University of the Basque Country (Grupo de Investigacion GIU17/054 and SGIker), Gobierno de Espana (Ministerio de Economia y Competitividad CTQ2016-77970-R, CTQ2017-83486-P and FPU16/04162), Gobierno Vasco (BERC program). 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 agreements 722951 and 714122).

Acenes have received a lot of attention because of their inherent and tunable absorbing, emissive, and charge transport properties for electronic, photovoltaic, and singlet fission applications, among others., Acenes have received a lot of attention because of their inherent and tunable absorbing, emissive, and charge transport properties for electronic, photovoltaic, and singlet fission applications, among others. Such properties are directly governed by molecular packing, and therefore, controlling their arrangement in the solid state is of utmost importance in order to increase their performance. Herein, we describe a new solid-state ordering strategy that allows obtaining 1D mixed π-stacks of acene and azaacene derivatives. In addition, we illustrate that charge transport can be modulated by the electronic nature of the encapsulated phenazine, opening new perspectives in the design, preparation and development of supramolecular organic semiconductors.

Polycyclic aromatic hydrocarbons that extend over 2 nm in one dimension are seen as monodisperse graphene nanoribbons, which have attracted significant attention for a broad range of applications in organic electronics and photonics. Herein we report the synthesis of a stable bisthiadiazole-capped pyrene-containing nanoribbon with 18 linearly fused rings (NR-18-TD). Thanks to the presence of alternating tert-butyl and tri-iso-butylsilyl groups, NR-18-TD is highly soluble in organic solvents and therefore its structure and fundamental optoelectronic, redox and electrical properties could be unambiguously established. This work illustrates that NR-18-TD is a promising soluble NR-based n-type semiconductor for applications in organic electronics. The authors are grateful to the Basque Science Foundation for Science (Ikerbasque), POLYMAT, the University of the Basque Country (Grupo de Investigación GIU17/054 and SGIker), Gobierno de España (Ministerio de Economía y Competitividad CTQ2016-77970-R and CTQ2015-71936-REDT), Gobierno Vasco (BERC program), CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT ref. UID/CTM/50011/2013), Diputación Foral de Guipúzcoa (OF215/2016(ES)) and the FP7 framework program of the European Union (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 also received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement no. 722951)

In this work, we report on the interaction of a tyrosinate radical with single wall carbon nanotubes (CNT). The tyrosinate radical was formed from tyrosine (ester) by Fenton's reagent and, reacted in situ with carbon nanotubes resulting in novel tyrosinated carbon nanotube derivatives. The covalent attachment of tyrosine on the external surface of the CNTs resulted in the appearance of a free radical, localized in the graphitic surface. The 'electron injection' (delocalization) of the free radical from the tyrosine ring onto the carbon nanotubes was studied and characterized by a combination of electron paramagnetic resonance, Raman and X-ray photoelectron spectroscopies, thermogravimetric analysis, as well as transmission electron and atomic force microscopies. The experiments, complemented by computer simulations, give insight into the formation process and structural details of the produced hybrid structures. (C) 2013 Elsevier Ltd. All rights reserved.

The reactivity of a fullerene-stoppered rotaxane, a C60 monoadduct, towards a second cycloaddition reaction is explored. The close proximity of the macrocycle to the fullerene sphere is able to allosterically influence the second cycloaddition reaction, giving rise to a selected mixture of bis-adducts.

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 pyrene-fused phenazinothiadiazole that shows electron mobilities (μe= 0.016 cm2V−1s−1) two orders of magnitude higher than those reported for pyrene-fused pyrazaacenes is described.

The synthesis, optoelectronic properties and near-infrared electroluminescent heterojunctions of a twisted and soluble 7,8,15,16,23,24-hexaazatrianthrylene derivative are reported.

Semiconductor organometallic halide (CH 3 NH 3 PbX 3 , X=Cl, Br, I) perovskites (HPVK) have been emerged as a potential gain media to construct a new generation of active photonic devices. Indeed, during the last three years a significant effort has been carried out to implement HPVK-based optical amplifiers or lasers with improved quality factors. In particular, minimization of the threshold of stimulated emission has been an important concern to decrease the power consumption, and hence to enhance the performances of the device. For this purpose strategies include a suitable integration of the semiconductor in a photonic structure, or the optimization of the material. Here we propose a novel approach to develop optical amplifiers by an appropriate passivation of HPVK layers incorporated in an optical waveguide. For this purpose, geometrical parameters were firstly properly optimized to demonstrate amplification of stimulated emission with a threshold as a low as 2 nJ. In addition, the passivation of traps of the semiconductor by introducing organic additives (twisted hexaazatrinaphthylene and bisthiadiazolefused tetraazapentacenequinone) resulted in a further reduction of the threshold (down to four fold). These results provide a novel scheme to enhance the applications of perovskite active devices.

The synthesis and properties of 11,11,12,12-tetracyano-4,5-pyrenoquinodimethanes (4,5-TCNPs), a new family of isolable and air-stable o-quinodimethanes, are reported. The ortho disposition of the dicyanomethane substituents strongly polarizes the pyrene framework to promote broad and intense intramolecular charge-transfer transitions. In addition, spectroscopic studies reveal that 4,5-TCNPs violate Kasha’s rule and emit from the S2 level., Fundação para a Ciência e a Tecnologia (FCT)

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. We are grateful to the Basque Science Foundation for Science (Ikerbasque), POLYMAT, the University of the Basque Country (SGIker), the Deutsche Forschungsgemeinschaft (AU 373/3-1 and MA 5215/4-1), Gobierno de Espana/FEDER (Ministerio de Economia y Competitividad, CTQ2015-71936-REDT, CTQ2016-77970-R, and ENE2015-66975-C3), Gobierno Vasco (BERC program, PC2015-1-01(06-37), and IT1069-16), Diputacion Foral de Guipuzkoa (2015-CIEN-000054-01), CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT ref. UID/CTM/50011/ 2013), ON2 (NORTE-07-0162-FEDER-000086), the Fund of Scientific Research-Flanders (FWO), the Internal Funds KU Leuven, the Belgian Federal Science Policy Office (IAP-7/05), and the Nanoscale and Microscale Research Centre (NMRC, University of Nottingham, UK) for access to TEM. We have received funding for the research leading to these results from the European Union Seventh Framework Programme as a European Research Area Action (ERA-Chemistry) and a Marie Curie Action (Career Integration Grant No. 618247) and from the European Union Framework Programme for Research and Innovation Horizon 2020 as a Future and Emerging Technologies Action (FET Open) under Grant Agreement No. 664878 (2D-INK).

The synthesis and properties of two highly stable K-conjugated dibenzoazahexacenes are reported. Single-crystal X-ray, optoelectronic, and electrochemical characterization combined with theoretical studies show a favorable molecular packing and an optimal energy alignment of their frontier orbitals for charge transport. Electrical characterization illustrates that the preferential transport of holes or electrons depends on the number of N atoms in the aromatic framework.

A new synthetic route to prepare a series of versatile 2,7-substituted pyrene synthons for the synthesis of pyrene-fused azaacenes is described. By using such synthons, a library of eight pyrene-fused azacenes with different electronic structures and in most cases with enhanced solubility has been synthesized and characterized.

Single-wall carbon nanotubes (SWNTs) are emerging as materials with much potential in several disciplines, in particular in electronics and photovoltaics. The combination of SWNTs with electron donors or acceptors generates active materials, which can produce electrical energy when irradiated. However, SWNTs are very elusive species when characterization of their metastable states is required. This problem mainly arises because of the polydispersive nature of SWNT samples and the inevitable presence of SWNTs in bundles of different sizes. Here, we report the complete and thorough characterization of an SWNT radical ion-pair state induced by complexation with a perylene dye, which combines excellent electron-accepting and -conducting features with a five-fused ring π-system. At the same time, the perylene dye enables the dispersion of SWNTs by means of π-π interactions, which gives individual SWNTs in solution. This work clears a path towards electronic and optoelectronic devices in which regulated electrical transport properties are important.