Gunther Hennrich

Organic Semiconductors toward Electronic Devices: High Mobility and Easy Processability

Chemists worldwide are making strong efforts toward finding an organic semiconductor with optimum charge-transport stability and processability properties, approaching the problem from several angles. The number and variety of organic semiconductors have expanded exponentially during the past few years, allowing their classification and identification of the advantages and drawbacks of the different candidates, and leading to an increasingly better understanding of factors affecting charge carrier mobility. In this Perspective, we present different types of materials available, classified according to their supramolecular order. As it will be shown, high intermolecular order, although beneficial for charge transport, may compromise processability. The required balance between processing and high mobility can be achieved only through an adequate design at both the molecular and supramolecular levels.

Self-Assembly of C3-Symmetrical Hexaaryltriindoles Driven by Solvophobic and CH―π Interactions

The synthesis and aggregation properties of a series of differently substituted star-shaped hexaaryltriindoles both in solution and in the solid state are being reported. While these molecules do not show any significant intermolecular aggregation in CDCl(3), it has been possible to induce aggregation by increasing the polarity of the solvent and therefore facilitating the occurrence of solvophobic forces. A study of the influence of the electronic character of peripheral substituents on the self-association behavior in solution has shown that increasing the electron-donor character of the substituents facilitates self-association while derivatives substituted with electron-acceptor substituents do not self-assemble. The electronic nature of the substituents also has an influence in the geometry of the stacking of these derivatives observed in the solid state. While unsubstituted hexaphenyl triindole self-assemble in a staggered face-to-face arrangement, attaching six cyano functional groups results in an offset stacking. The influence of the substituents in the strength and geometry of the stacking tendency contrasts with the trend expected for an aggregation induced solely by pi-pi interactions, but can be explained considering an important contribution of multiple cooperative CH-pi interactions.

Synthesis, Spectroscopy, Nonlinear Optics, and Theoretical Investigations of Thienylethynyl Octopoles with a Tunable Core

We have synthesized three new molecules that have three thienylethynyl arms substituting a central benzene core and different electron donor/acceptor groups in the three remaining phenyl positions. The absorption, fluorescence, phosphorescence, and transient triplet-triplet spectra are analyzed in the light of the electronic structure of the ground and excited states obtained from quantum-chemical calculations. From the above, the relevant photophysical data (including quantum yields, lifetimes, and rate constants) could be derived. It was found that the major deactivation pathway is internal conversion, which competes with the fluorescence and intersystem crossing processes. For the three investigated compounds, we provide convincing theoretical support corroborating these findings and further conclusions based on the theoretical information obtained. These molecules are one of the very few cases in which the depolarization ratios, obtained from the NLO optical measurements, clearly reflect the octopolar configuration. Molecular hyperpolarizabilities have been measured and display a typical dependence on the donor-acceptor substitution pattern.

Solvent‐Dependent Truxene‐Based Nanostructures

Three truxene derivatives functionalized with alkyl chains, either attached directly or distanced by linking phenyl or ethynyl groups, self-assemble in solution and induce the gelation of different solvents in spite of not being endowed with groups able to establish strong directional interactions. A (1)H NMR study points to face-to-face alternating π-stacked motifs at the origin of nucleation. Solvents play an important role in modulating the aggregation of these derivatives giving rise to fibrous or spherical superstructures. Analysis of the influence of different solvents on the morphology of the aggregates provides a better understanding of the various stages of the hierarchical self-assembly. The way in which alkyl chains are attached to the central core also strongly affects the self-assembling properties and gelation ability of this series. Phenyl spacers present the highest association constants in solution and give rise to gelation in a broader range of solvents. This behavior has been rationalized by means of (1)H NMR spectroscopy, X-ray powder diffraction, SEM, and photophysical measurements. Interestingly, it was found that these compounds in the gel state exhibit unusual emission properties most likely arising from the formation of excimers, which evidences that π-π interactions also occur in the excited state.

Nonlinear Optical Thin Film Device from a Chiral Octopolar Phenylacetylene Liquid Crystal

A set of chiral discotic phenylacetylenes have been synthesized by 3-fold Sonogashira coupling between different ethynylbenzenes and triiodobenzenes. The resultant bulk materials are fully characterized by polarized optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray diffraction. The octopolar nature of the target compounds is studied by UV-vis absorption spectroscopy and hyper-Raleigh scattering in solution. Optimization of the donor-acceptor substitution yields both high hyperpolarizability values and appreciable mesomorphic properties. A simple thin film device for second harmonic generation has been prepared from the nitro-substituted liquid crystalline derivative.

Tetraalkynyl calix[4]arenes with advanced NLO properties.

Rigid, highly conjugated tetraalkynyl-calix[4]arenes synthesised via Sonogashira coupling give rise to improved second-order hyperpolarizability values as determined by hyper-Rayleigh scattering--a technique that in addition to X-ray crystallography also allows for the conformational analysis of the calixarene structures in solution.

Aggregation behavior of a conjugated C3-symmetric molecule: a description based on chiro-optical experimental and theoretical spectroscopies.

A new chiral octopolar C(3)-symmetric molecule is synthesized and its optical and chiro-optical properties are analyzed with the help of density functional theory. In all the cases, the work relates these spectroscopic properties with the phenomena of aggregation. Ultraviolet-visible absorption, infrared and Raman spectroscopies, and ECD and VCD chiro-optical spectroscopies are presented in combination with theoretical chemistry. In this regard, optical spectroscopies are insensitive to the supramolecular effects, while electronic and vibrational circular dichroism spectroscopies delivered adequate proof for the detection of aggregation. We have simulated the effect of molecular self-assembly by means of a docking process that provides a stable dimer on which all the spectroscopic properties have been theoretically calculated. The shape of this dimer provides us with a guideline to propose a helicoidal aggregate that is the responsibility of the chiro-optical spectra amplified by self-assembly.

Magneto-optical activity in organic thin film materials

A series of CF3-capped phenylacetylenes with varying symmetry is obtained by a conventional palladium-catalyzed cross-coupling protocol. The phenylacetylene targets form thin films both, liquid crystalline (LC) and crystalline in nature depending on their molecular structure. The magneto-optical activity of the resulting organic material is extraordinarily high as proved by Faraday rotation spectroscopy on thin film devices.

High‐Mobility Self‐Assembling Truxenone‐Based n‐Type Organic Semiconductors

The synthesis, self-assembly, and semiconducting properties of a series of disk-like truxenone derivatives, functionalized with three peripheral long alkyl chains, either directly attached or distanced by linking phenyl or ethynyl groups, are reported. The strategy of distancing the alkyl chains from the central aromatic cores induces in these discotics well-ordered columnar assemblies and has a favorable effect on their charge-carrier mobility. Electron mobility values above 1 cm2  V-1  S-1 were determined for a truxenone functionalized with three peripheral decynyl chains by means of the space charge-limited current technique. DFT calculations help to rationalize the high mobility values found for these new truxenone-based systems, indicating efficient intermolecular electronic couplings (fostered by a favorable stacking configuration) and moderate intramolecular reorganization energies for electrons in the origin of such high mobilities.

Spontaneous chirality in an octupolar discotic crystal

In the quest for organic second-order nonlinear materials, self-assembled structures based on octupolar molecules have shown to be promising candidates. The presented work focuses on an octupolar substituted 1,3,5-trisalkynylbenzene that forms crystals that show significant second-harmonic generation (SHG). Continuous polarization SHG measurements were performed to elucidate the tensorial nature of this response. Unfortunately the model at hand was unable to fit the polarization patterns due to depolarization of the second harmonic beam caused by multiple scattering in the sample. Although the chromophore is clearly achiral, these patterns revealed a different response for left and right circularly polarized light, also known as SHG circular difference. This implies that these molecules spontaneously assemble in chiral superstructures. These surprising results were confirmed by circular dichroism spectroscopy, revealing a monosignate CD band that must be attributed to a supramolecular chiral organization.