Di‐ and Tetracyano‐Substituted Pyrene‐Fused Pyrazaacenes: Aggregation in the Solid State

Means to stream: Five di- and tetracyano-substituted pyrene-fused pyrazaacenes were synthesized and studied as potential electron acceptors in the solid state. Single crystals of all compounds were grown, and the crystal packing was studied by XRD and DFT calculations of transfer integrals and reorganization energies with a view to their possible use as n-type semiconductors. Five di- and tetracyano-substituted pyrene-fused pyrazaacenes were synthesized and studied as potential electron acceptors in the solid state. Single crystals of all compounds were grown and the crystal packing studied by DFT calculations (transfer integrals and reorganization energies) to get insight into possible use for semiconducting charge transport

Quinoxalinophenanthrophenazine Based Cruciforms

Quinoxalinophenanthrophenazines (QPPs) and related structures are an emerging class of stable fused N-heteropolycyclic aromatics. By vertical attachment of aromatic substituents at the pyrene core, cruciform QPPs are accessible, which open new opportunities to adjust HOMO and LUMO levels of the QPPs nearly independent from each other. A series of cruciform aryl-substituted quinoxalinophenanthrophenazine derivatives (QPPs) was synthesized through Suzuki-Miyaura cross-coupling of a 2,7-diborylated pyrene tetraketal building block. The QPPs were analyzed for their optoelectronic properties by absorption and emission spectroscopy, cyclic voltammetry and quantum-chemical calculations. The solid-state packing was investigated as well and evaluated for its charge transport properties by calculated charge transfer integrals

Triptycene End‐Capped Benzothienobenzothiophene and Naphthothienobenzothiophene

Previously it was demonstrated that triptycene end‐capping can be used as a crystal engineering strategy to direct the packing of quinoxalinophenanthrophenazines (QPPs) towards cofacially stacked π dimers with large molecular overlap resulting in high charge transfer integrals. Remarkably, this packing motif was formed under different crystallization conditions and with a variety of derivatives bearing additional functional groups or aromatic substituents. Benzothienobenzothiophene (BTBT) and its derivatives are known as some of the best performing compounds for organic field‐effect transistors. Here, the triptycene end‐capping concept is introduced to this class of compounds and polymorphic crystal structures are investigated to evaluate the potential of triptycene end‐caps as synthons for crystal engineering

Two Dimensional Triptycene End‐Capping and Its Influence on the Self‐Assembly of Quinoxalinophenanthrophenazines †

In this report we investigated two-dimensionally triptycene end-capped QPPs in terms of their solution and solid-state behavior. For this purpose, a triphenylene based ortho-diamine decorated with two triptycenyl units as well as a phenylene diamine with two non-annulated triptycene units have been synthesized. Sequences of condensation reactions with a pyrene-based tetraketone and ortho-diamines yielded a series of QPPs and UV/Vis investigations of the corresponding compounds led to the conclusion, that the QPPs form dimers in solution, which was further supported by MALDI-TIMS-TOF-MS. Single-crystal X-ray analysis of the triply and quadruply triptycene end-capped QPPs furthermore showed short π-π-distances of 3.3—3.4 Å and a perfect shape match during the dimerization of the triply triptycenyl end-capped QPP making it possible synthon fo

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

Evaluating the Effects of Geometry and Charge Flux in Force Field Modeling

We apply a model for analyzing the importance of conformational charge flux to 11 molecules with the R–(CH₂)_<i>n</i>–R structure (R = Cl, F, OH, SH, COOH, CONH₂, and NH₂ and <i>n</i> = 4–6). Atomic charges were obtained by fitting to results from density functional theory calculations using the HLY procedure, and their geometry dependence is decomposed into contributions from changes in bond lengths, bond angles, and torsional angles. The torsional degrees of freedom are the main contribution to the conformational dependence of atomic charges and molecular dipole moments, but indirect effects due to changes in bond distances and angles account for ∼15% of the variations. While the magnitude of charge flux and geometry effects have been found to be independent of the number of internal degrees of freedom, the nature of the R- group has a moderate influence. The indirect effects are comparable for all of the R-groups and are approximately one-half the magnitude of the corresponding effects in peptide models. However, the magnitudes are different, yet the relative importance of geometry and charge flux effects are completely similar to those of the peptide models, which suggests that modeling the charge flux effects for changes in bond lengths, bond angles, and torsional angles should be considered for developing improved force fields

Evaluating the Effects of Geometry and Charge Flux in Force Field Modeling

We apply a model for analyzing the importance of conformational charge flux to 11 molecules with the R–(CH₂)_<i>n</i>–R structure (R = Cl, F, OH, SH, COOH, CONH₂, and NH₂ and <i>n</i> = 4–6). Atomic charges were obtained by fitting to results from density functional theory calculations using the HLY procedure, and their geometry dependence is decomposed into contributions from changes in bond lengths, bond angles, and torsional angles. The torsional degrees of freedom are the main contribution to the conformational dependence of atomic charges and molecular dipole moments, but indirect effects due to changes in bond distances and angles account for ∼15% of the variations. While the magnitude of charge flux and geometry effects have been found to be independent of the number of internal degrees of freedom, the nature of the R- group has a moderate influence. The indirect effects are comparable for all of the R-groups and are approximately one-half the magnitude of the corresponding effects in peptide models. However, the magnitudes are different, yet the relative importance of geometry and charge flux effects are completely similar to those of the peptide models, which suggests that modeling the charge flux effects for changes in bond lengths, bond angles, and torsional angles should be considered for developing improved force fields

Modeling Exciton Transport in Organic Semi-conductors Using Machine Learned Hamiltonian and its Gradients

In this study, we present a multiscale method to simulate the propagation of Frenkel singlet excitons in Organic Semi-conductors(OSCs). The approach uses advanced neural network models to train Frenkel-type Hamiltonian and its gradient, obtained by the Long-Range Correction version of Density Functional Tight-Binding with Self-Consistent Charges (LC-DFTB2). Our models accurately predict site energies, excitonic couplings, and corresponding gradients, essential for the non-adiabatic molecular dynamics simulations. Combined with Fewest Switches Surface Hopping (FSSH) algorithm, the method was applied to four representative OSCs: Anthracene (ANT), Pentacene (PEN), Perylenediimide (PDI), and Diindenoperylene (DIP). The simulated exciton diffusion constants align well with experimental and reported theoretical values, and offer valuable insights into exciton dynamics in OSCs

Di‐ and Tetracyano‐Substituted Pyrene‐Fused Pyrazaacenes: Aggregation in the Solid State

Means to stream: Five di- and tetracyano-substituted pyrene-fused pyrazaacenes were synthesized and studied as potential electron acceptors in the solid state. Single crystals of all compounds were grown, and the crystal packing was studied by XRD and DFT calculations of transfer integrals and reorganization energies with a view to their possible use as n-type semiconductors. Five di- and tetracyano-substituted pyrene-fused pyrazaacenes were synthesized and studied as potential electron acceptors in the solid state. Single crystals of all compounds were grown and the crystal packing studied by DFT calculations (transfer integrals and reorganization energies) to get insight into possible use for semiconducting charge transport