Tunable Regioselectivity in C-H-Activated Direct Arylation Reactions of Dithieno[3,2-b:2',3'-d]pyrroles.

In this study, regioselectively controlled direct arylation of dithieno[3,2-b:2,3'-d]pyrroles (DTPs) is reported. By carefully selecting the catalytic system, Pd source, ligand, and additives, we achieved either selective N-arylation or unprecedented ß-arylation and ß,ß'-diarylation of the DTP core through C-H activation when reacting unsubstituted H-DTP with 9-anthracenyl halides. For N-substituted DTPs, we obtained regioselective carboxylate-assisted arylation of the α-position(s). Consequently, depending on the catalytic system and substitution at the DTP nitrogen, we successfully synthesized novel regioselectively substituted DTPs, including N-aryl, rarely reported ß-aryl, ß,ß'-diaryl, α-aryl, and α,α'-diaryl scaffolds. These compounds can be straightforwardly prepared and further functionalized for applications as organic electronic materials.

Molecular Donor-Acceptor Dyads for Single-Material Organic Solar Cells.

A series of ambipolar covalently linked oligothiophene-fullerene dyads have been synthesized by systematical structural variations. In this respect, the length of linker between donor and acceptor unit was altered and in a second series the terminal acceptor units in the donor unit of the dyads were varied. Characterization of the optical and redox properties gave valuable structure-property relationships and were correlated to the photovoltaic performance in single-material organic solar cells, in which power conversion efficiencies of up to 4.3 % were reached.

Highly Crowded Twisted Thienylene-Phenylene Structures: Evidence for Through-Space Orbital Coupling in a [4]Catenated Topology.

Sterically highly crowded and twisted thienylene-phenylenes are synthesized and structurally characterized. Single-crystal X-ray structure analyses and theoretical studies give evidence of through-space delocalization of π-electrons of peripheral (hetero)aromatic rings in toroidal and catenated topology.

Molecular Oligothiophene-Fullerene Dyad Reaching Over 5% Efficiency in Single-Material Organic Solar Cells.

A novel donor-acceptor dyad, 4, in which the conjugated oligothiophene donor is covalently connected to fullerene PC71 BM by a flexible alkyl ester linker, is synthesized and applied as photoactive layer in solution-processed single-material organic solar cells (SMOSCs). Excellent photovoltaic performance, including a high short-circuit current density (JSC ) of 13.56 mA cm-2 , is achieved, leading to a power conversion efficiency of 5.34% in an inverted cell architecture, which is substantially increased compared to other molecular single materials. Furthermore, dyad 4-based SMOSCs display excellent stability maintaining 96% of the initial performance after 750 h (one month) of continuous illumination and operation under simulated AM 1.5G irradiation. These results will strengthen the rational molecular design to further develop SMOSCs for potential industrial application.

Broadly Applicable Synthesis of Arylated Dithieno[3,2-b:2',3'-d]pyrroles as Building Blocks for Organic Electronic Materials.

A novel and versatile method for the N-arylation of dithieno[3,2-b:2',3'-d]pyrrole (DTP) is presented. By Pd- or Cu-catalyzed coupling a variety of arenes and acenes were directly attached at the DTP-nitrogen yielding a variety of functionalized DTPs. Investigations on optical and redox properties led to valuable structure-property relationships, which were corroborated by quantum chemical calculations. Further functionalization and elongation of the conjugation of an acceptor-substituted DTP was elaborated to result in complex cruciform-type donor-acceptor oligomers, which were investigated and implemented in single material organic solar cells.

Advanced Acceptor-Substituted S,N-Heteropentacenes for Application in Organic Solar Cells.

Ambifunctional heterpentacenes with the heteroatom sequence SSNSS in the ladder-type backbone were used either as donor or as nonfullerenic acceptor in solution-processed bulk-heterojunction solar cells. Different acceptor moieties and side chains were inserted. Synthesis and characterization of the systematically varied structural motifs provided insight in structure-property relationships. Moreover, a dimeric heteroacene was synthesized, and the optoelectronic properties were compared to those of its monomeric counterpart.

Intermolecular conical intersections in molecular aggregates.

Conical intersections (CoIns) of multidimensional potential energy surfaces are ubiquitous in nature and control pathways and yields of many photo-initiated intramolecular processes. Such topologies can be potentially involved in the energy transport in aggregated molecules or polymers but are yet to be uncovered. Here, using ultrafast two-dimensional electronic spectroscopy (2DES), we reveal the existence of intermolecular CoIns in molecular aggregates relevant for photovoltaics. Ultrafast, sub-10-fs 2DES tracks the coherent motion of a vibrational wave packet on an optically bright state and its abrupt transition into a dark state via a CoIn after only 40 fs. Non-adiabatic dynamics simulations identify an intermolecular CoIn as the source of these unusual dynamics. Our results indicate that intermolecular CoIns may effectively steer energy pathways in functional nanostructures for optoelectronics.

Synthesis and characterization of S,N-heterotetracenes.

The synthesis and optoelectronic properties of novel S,N-heterotetracenes consisting of fused heterocyclic thiophene and pyrrole rings are presented. Tetracyclic and benzannulated derivatives with a varying number and sequence of sulfur and nitrogen heteroatoms were synthesized in multistep synthetic routes. A Buchwald-Hartwig amination of brominated precursors, thermolysis of azide precursors, and a Cadogan reaction of nitro-substituted precursors were successfully applied to eventually build-up pyrrole rings to stable and soluble fused systems. The various obtained heteroatom sequences 'SSNS' (SN4), 'SNNS' (SN4''), and 'NSSN' (SN4') allowed for evaluation of structure-property relationships relative to the sulfur analogue tetrathienoacene ('SSSS'). In line with the results for the whole series of S,N-heteroacenes, we find that replacement of sulfur by nitrogen atoms in the tetra- and hexacyclic systems leads to a red-shift in absorption, a decrease in oxidation potential and energy gap. On the other hand, the replacement of a thiophene ring by benzene leads to the opposite effects.

Self-Assembly, Adaptive Response, and in,out-Stereoisomerism of Large Orthoformate Cryptands.

We report on triethylene glycol-based orthoformate cryptands, which adapt their bridgehead configurations in response to metal templates and intramolecular hydrogen bonding in a complex manner. In contrast to smaller 1.1.1-orthoformate cryptands, the inversion from out,out-2.2.2 to in,in-2.2.2 occurs spontaneously by thermal homeomorphic isomerization, i. e., without bond breakage. The global thermodynamic minimum of the entire network, which includes an unprecedented third isomer (in,out-2.2.2), could only be reached under conditions that facilitate dynamic covalent exchange. Both inversion processes were studied in detail, including DFT calculations and MD simulations, which were particularly helpful for explaining differences between equilibrium compositions in solvents chloroform and acetonitrile. Unexpectedly, the system could be driven to the in,out-2.2.2 state by using a metal template with a size mismatch with respect to the out,out-2.2.2 cage.

Covalently linked donor-acceptor dyad for efficient single material organic solar cells.

A novel covalently linked donor-acceptor dyad comprising a dithienopyrrol-based oligomeric donor and a fullerene acceptor was synthesized and characterized. The concomitant effect of favorable optoelectronic properties, energy levels of the frontier orbitals, and ambipolar charge transport enabled the application of the dyad in simplified solution-processed single material organic solar cells reaching a power conversion efficiency of 3.4%.

Self-templated synthesis of an orthoformate in,in-cryptand and its bridgehead inversion by dynamic covalent exchange.

We report the template-free dynamic covalent self-assembly of a small orthoformate cryptand, which appears to be driven by the formation of two sets of intramolecular, four-centre hydrogen bonds. In contrast to their nitrogen-bridgehead counterparts, orthoformate cryptands do not spontaneously invert, but require dynamic covalent exchange to do so.

Selenophene-containing heterotriacenes by a C-Se coupling/cyclization reaction.

A new novel family of tricyclic sulfur and/or selenium-containing heterotriacenes 2-4 with an increasing number of selenium (Se) atoms is presented. The heterotriacene derivatives were synthesized in multistep synthetic routes and the crucial cyclization steps to the stable and soluble fused systems were achieved by copper-catalyzed C-S and C-Se coupling/cyclization reactions. Structures and packing motifs in the solid state were elucidated by single crystal X-ray analysis and XRD powder measurements. Comparison of the optoelectronic properties provides interesting structure-property relationships and gives valuable insights into the role of heteroatoms within the series of the heterotriacenes. Electrooxidative polymerization led to the corresponding poly(heterotriacene)s P2-P4.

Self-assembled orthoester cryptands: orthoester scope, post-functionalization, kinetic locking and tunable degradation kinetics.

Dynamic adaptability and biodegradability are key features of functional, 21st century host-guest systems. We have recently discovered a class of tripodal supramolecular hosts, in which two orthoesters act as constitutionally dynamic bridgeheads. Having previously demonstrated the adaptive nature of these hosts, we now report the synthesis and characterization - including eight solid state structures - of a diverse set of orthoester cages, which provides evidence for the broad scope of this new host class. With the same set of compounds, we demonstrated that the rates of orthoester exchange and hydrolysis can be tuned over a remarkably wide range, from rapid hydrolysis at pH 8 to nearly inert at pH 1, and that the Taft parameter of the orthoester substituent allows an adequate prediction of the reaction kinetics. Moreover, the synthesis of an alkyne-capped cryptand enabled the post-functionalization of orthoester cryptands by Sonogashira and CuAAC "click" reactions. The methylation of the resulting triazole furnished a cryptate that was kinetically inert towards orthoester exchange and hydrolysis at pH > 1, which is equivalent to the "turnoff" of constitutionally dynamic imines by means of reduction. These findings indicate that orthoester cages may be more broadly useful than anticipated, e.g. as drug delivery agents with precisely tunable biodegradability or, thanks to the kinetic locking strategy, as ion sensors.

Ferrocene-functionalized polyheteroacenes for the use as cathode active material in rechargeable batteries.

Herein we report the synthesis and characterization of new conjugated polymers bearing redox-active pendant groups for applications as cathode active materials in secondary batteries. The polymers comprise a ferrocene moiety immobilized at a poly(cyclopenta[2,1-b:3,4-b']dithiophene) (pCPDT, P1) or a poly(dithieno[3,2-b:2',3'-d]pyrrole) (pDTP, P2) backbone via an ester or an amide linker. Electrochemical and oxidative chemical polymerizations were performed in order to investigate the redox behaviour of the obtained polymers P1 and P2 and to synthesize materials on gram-scale for battery tests, respectively. During galvanostatic cycling in a typical battery environment, both polymers showed high reversible capacities of 90% and 87% of their theoretical capacity and excellent capacity retentions of 84% and 97% over 50 cycles.

Spectroscopic Study of Thiophene-Pyrrole-Containing S,N-Heteroheptacenes Compared to Acenes and Phenacenes.

In this study, we report a detailed spectroscopic study concerning the energy levels and vibrational structure of thiophene-pyrrole-containing S,N-heteroacenes. The aim of the study is first, to understand the differences in the photoluminescence (PL) efficiencies in this structurally similar series and second, to compare the electronic structure of S,N-heteroacenes to that of linear acenes and phenacenes, with a view to derive guidelines for the design of singlet fission materials. For S,N-heteroacenes comprising seven fused heterocyclic rings, we observe a higher PL quantum yield for derivatives with terminal thienothiophene units than for thienopyrrole-capped ones. This is assigned to a stronger tendency of the thienopyrrole-capped derivatives to form nonemissive associates in dilute solution, producing emissive excimers at higher concentration. By conducting time-resolved PL studies at 77 K, we further determine the lowest singlet and triplet energies for the S,N-heteroacenes with three, five, and seven fused rings. We show that their energies evolve with oligomer length analogously to those of phenacenes, yet in a fundamentally different way from that of linear acenes. This difference in evolution is attributed to the increasingly biradical character in acenes with increasing chain length in contrast to the S,N-heteroacenes and phenacenes.

Fused thiophene-pyrrole-containing ring systems up to a heterodecacene.

A new class of π-conjugated polycyclic hydrocarbons that promises interesting electronic properties is presented. The synthesis and extension of the S,N-heteroacene series consisting of only five-membered heterocyclic rings up to a very long, stable, and still soluble decacene SN10 is realized by multiple Pd-catalyzed aminations of halogenated thiophene precursors as key reactions. These novel heteroacenes were characterized by optical spectroscopy and electrochemistry providing interesting structure-property relationships. Nearly complete bond-length equalization in the inner part of the conjugated backbone and an unusual herringbone packing in the solid state underline the structural features of these novel systems.

π-Conjugated [2]Catenanes Based on Oligothiophenes and Phenanthrolines: Efficient Synthesis and Electronic Properties.

Novel π-conjugated topologies based on oligothiophenes and phenanthroline have been assembled by combining their outstanding electronic and structural benefits with the specific properties of the topological structure. Macrocycles and catenanes are prepared by using an optimized protocol of transition metal-templated macrocyclization followed by efficient Pd-catalyzed cross-coupling reaction steps. By using this method, [2]catenanes comprising two interlocked π-conjugated macrocycles with different ring sizes have been synthesized. The structures of the [2]catenanes and corresponding macrocycles are confirmed by detailed (1) H NMR spectroscopy and high resolution mass spectrometry. Single crystal X-ray structural analysis of the quaterthiophene-diyne macrocycle affords important insight into the packing features and intermolecular interaction of the new systems. The fully conjugated interlocked [2]catenanes are fully characterized by spectroscopic and electrochemical measurements.

A-D-A-type S,N-heteropentacenes: next-generation molecular donor materials for efficient vacuum-processed organic solar cells.

A new class of acceptor-substituted S,N-heteropentacenes is developed for vacuum-processed organic solar cells, providing encouraging power conversion efficiencies of up to 6.5%. Atomic force microscopy (AFM) investigations give a direct correlation between the blend film morphology and the photovoltaic parameters, such as short-circuit current density (JSC ) and fill factor (FF).

Orbital redistribution in molecular nanostructures mediated by metal-organic bonds.

Dicyanovinyl-quinquethiophene (DCV5T-Me2) is a prototype conjugated oligomer for highly efficient organic solar cells. This class of oligothiophenes are built up by an electron-rich donor (D) backbone and terminal electron-deficient acceptor (A) moieties. Here, we investigated its structural and electronic properties when it is adsorbed on a Au(111) surface using low temperature scanning tunneling microscopy/spectroscopy (STM/STS) and atomic force microscopy (AFM). We find that DCV5T-Me2 self-assembles in extended chains, stabilized by intercalated Au atoms. The effect of metal-ligand hybridization with Au adatoms causes an energetic downshift of the DCV5T-Me2 lowest unoccupied molecular orbital (LUMO) with respect to the uncoordinated molecules on the surface. The asymmetric coordination of a gold atom to only one molecular end group leads to an asymmetric localization of the LUMO and LUMO+1 states at opposite sides. Using model density functional theory (DFT) calculations, we explain such orbital reshaping as a consequence of linear combinations of the original LUMO and LUMO+1 orbitals, mixed by the attachment of a bridging Au adatom. Our study shows that the alignment of molecular orbitals and their distribution within individual molecules can be modified by contacting them to metal atoms in specific sites.

Synthesis and structural analysis of thiophene-pyrrole-based S,N-heteroacenes.

Fused S,N-heterohexacene 4 was synthesized by applying Pd-catalyzed tandem Buchwald-Hartwig coupling and further functionalized to corresponding acceptor-capped derivatives 5 and 6 showing bond length equalization in the π-conjugated backbone and intense optical transitions. Organic thin film transistors (OTFTs) based on a vacuum-deposited film of 6 exhibit p-channel charge-carrier mobilities as high as 0.021 cm(2) V(-1) s(-1) and current on/off ratios of 10(5).