Wall Microstructures of High Aspect Ratio Enabled by Near‐Field Electrospinning

Near-field electrospinning (NFES) holds the potential to develop into a versatile additive nanomanufacturing platform. However, the impact of a variety of processing variables remains unresolved.Herein, the effect of solvents used to prepare suitable solutions for 3D microstructuring by electrospinning is studied. 3D straight walls of stacked fibers are fabricated using a layer-by-layer fiber deposition approach. The effect of the choice of substrate material is also explored. The results show that a high vapor pressure, and a low dielectric constant of the solvent, as well as a high substrate conductivity facilitate improved stacking of fiber layers. Utilizing these conditions, 3D stacked walls of polyethylene oxide are fabricated, and a maximum aspect ratio of 191.7 ± 52.6, while using a chromium/gold substrate and dichloromethane/methanol as the solvent is achieved

Three unique coordination geometries involving 1,2-dimethoxy-4,5-bis(2-pyridylethynyl)benzene

Reaction of the new ligand 1,2-dimethoxy-4,5-bis(2-pyridylethynyl) benzene with different metal centers under similar reaction conditions led to three distinct structure formation processes: molecular ring closure, dimerization, and polymer formation

Functionalized tetrapodal diazatriptycenes for electrostatic dipole engineering in n-type organic thin film transistors

V.R., F.S.B., S.H., M.M., M.-M.B., S.H., J.F., W.K., W.J., A.K., A.P., U.H.F.B., and K.M. acknowledge the German Federal Ministry of Education and Research (BMBF) for financial support within the INTERPHASE project (nos. 13N13656, 13N13657, 13N13658, 13N13659). V.R. thanks the German Research Foundation for financial support within the SFB1249 project and the Heidelberg Graduate School of Fundamental research.The authors also appreciate financial support by the German Research Foundation (grant ZH 63/39-1) and by the DAAD-ACEH Scholarship of Excellence (A.A.).A diazatriptycene‐based tetrapodal scaffold with thiol anchors enforces a nearly upright orientation of functional groups, introduced to its quinoxaline subunit, with respect to the substrate upon formation of self‐assembled monolayers (SAMs). Substitution with electron‐withdrawing fluorine and cyano as well as electron‐rich dimethylamino substituents allows tuning of the molecular dipole and, consequently, of the work function of gold over a range of 1.0 eV (from 3.9 to 4.9 eV). The properties of the SAMs are comprehensively investigated by infrared reflection absorption spectroscopy, near edge X‐ray absorption fine structure spectroscopy, and X‐ray photoelectron spectroscopy. As prototypical examples for the high potential of the presented SAMs in devices, organic thin‐film transistors are fabricated.Publisher PDFPeer reviewe

Interplay of structural dynamics and electronic effects in an engineered assembly of pentacene in a metal–organic framework

Charge carrier mobility is an important figure of merit to evaluate organic semiconductor (OSC) materials. In aggregated OSCs, this quantity is determined by inter-chromophoric electronic and vibrational coupling. These key parameters sensitively depend on structural properties, including the density of defects. We have employed a new type of crystalline assembly strategy to engineer the arrangement of the OSC pentacene in a structure not realized as crystals to date. Our approach is based on metal–organic frameworks (MOFs), in which suitably substituted pentacenes act as ditopic linkers and assemble into highly ordered π-stacks with long-range order. Layer-by-layer fabrication of the MOF yields arrays of electronically coupled pentacene chains, running parallel to the substrate surface. Detailed photophysical studies reveal strong, anisotropic inter-pentacene electronic coupling, leading to efficient charge delocalization. Despite a high degree of structural order and pronounced dispersion of the 1D-bands for the static arrangement, our experimental results demonstrate hopping-like charge transport with an activation energy of 64 meV dominating the band transport over a wide range of temperatures. A thorough combined quantum mechanical and molecular dynamics investigation identifies frustrated localized rotations of the pentacene cores as the reason for the breakdown of band transport and paves the way for a crystal engineering strategy of molecular OSCs that independently varies the arrangement of the molecular cores and their vibrational degrees of freedom

Singlet exciton fission in a modified acene with improved stability and high photoluminescence yield

Abstract: We report a fully efficient singlet exciton fission material with high ambient chemical stability. 10,21-Bis(triisopropylsilylethynyl)tetrabenzo[a,c,l,n]pentacene (TTBP) combines an acene core with triphenylene wings that protect the formal pentacene from chemical degradation. The electronic energy levels position singlet exciton fission to be endothermic, similar to tetracene despite the triphenylenes. TTBP exhibits rapid early time singlet fission with quantitative yield of triplet pairs within 100 ps followed by thermally activated separation to free triplet excitons over 65 ns. TTBP exhibits high photoluminescence quantum efficiency, close to 100% when dilute and 20% for solid films, arising from triplet-triplet annihilation. In using such a system for exciton multiplication in a solar cell, maximum thermodynamic performance requires radiative decay of the triplet population, observed here as emission from the singlet formed by recombination of triplet pairs. Combining chemical stabilisation with efficient endothermic fission provides a promising avenue towards singlet fission materials for use in photovoltaics

A fluorescent microporous crystalline dendrimer discriminates vapour molecules

A self-assembled crystalline microporous dendrimer framework (MDF) exhibits novel turn-on and ratiometric fluorescence upon exposure to solvent vapours. The donor–acceptor character, combined with the large surface area (>650 m2 g−1), allows the MDF to discriminate vapours of volatile solvents with turn-on and colour change of photoluminescence

n-type doping of organic semiconductors : immobilization via covalent anchoring

We gratefully acknowledge the German Federal Ministry of Education and Research (BMBF) for financial support within the InterPhase project (FKZ 13N13659, 13N13656, 13N13657, and 13N13658).Electrical doping is an important tool in the design of organic devices to modify charge carrier concentration in and Fermi level position of organic layers. The undesired diffusion of dopant molecules within common transport materials adversely affects both lifetime and device performance. To overcome this drawback, we developed a strategy to achieve immobilization of dopants through their covalent attachment to the semiconductor host molecules. Derivatization of the commonly employed n-type dopant 2-(2-methoxyphenyl)-1,3-dimethyl-2,3-dihydro-1H-benzoimidazole (ο-MeO-DMBI) with a phenylazide enables the resulting o-AzBnO-DMBI to photochemically generate a reactive nitrene, which subsequently binds covalently to the host material, 6,6-phenyl-C61-butyric acid methyl ester (PCBM). Both the activation and addition reactions are monitored by mass spectrometry as well as optical and photoelectron spectroscopy. A suppression of desorption and a decrease in volatility of the DMBI derivative in ultrahigh vacuum were observed after activation of a bilayer structure of PCBM and o-AzBnO-DMBI. Electrical measurements demonstrate that the immobilized o-AzBnO-DMBI can (i) dope the PCBM at conductivities comparable to values reported for o-MeO-DMBI in the literature and (ii) yield improved electrical stability measured in a lateral two terminal device geometry. Our immobilization strategy is not limited to the specific system presented herein but should also be applicable to other organic semiconductor–dopant combinations.Publisher PDFPeer reviewe

Cruciform fluorophores

Issued as final reportNational Science Foundation (U.S.

Synthesis of novel liquid crystalline organometallic polymers

Abstract; The synthesis and some properties of organometallic homo-and copolymers carrying diethynylated n-complexes are discussed. As monomers the diethynylated derivatives of cymantrene and cyclopentadienyl( 1,3-bistrimethylsilylcyc1obutadiene)cobalt were utilized. Novel thermotropic nematic and lyotropic smectic liquid crystalline polymers were synthesized as copolymers of 1 and 2,5-dihexyl-1 &diiodobenzene or 3-hexyl-2,5-diiodothiophene in a CassarHeck-Hagihara coupling reaction. The liquid crystalline behavior was secured by polarizing microscopy and powder X-ray diffractometry. Introduction Organometallic polymers hold a great future (academic) potential for the synthesis of materials with attractive properties such as liquid crystallinity, redox activity and electroresponsive behavior as well as NLO activity We have an interest in synthesis and chemistry of multiply ethynylated n-complexes which led to th