Synthesis of Poly(benzothiadiazole‐co‐dithienobenzodithiophenes) and Effect of Thiophene Insertion for High‐Performance Polymer Solar Cells

We describe herein the synthesis of novel donor–acceptor conjugated polymers with dithienobenzodithiophenes (DTBDT) as the electron donor and 2,1,3‐benzothiadiazole as the electron acceptor for high‐performance organic photovoltaics (OPVs). We studied the effects of strategically inserting thiophene into the DTBDT as a substituent on the skeletal structure on the opto‐electronic performances of fabricated devices. From UV/Vis absorption, electrochemical, and field‐effect transistor analyses, we found that the thiophene‐containing DTBDT derivative can substantially increase the orbital overlap area between adjacent conjugated chains and thus dramatically enhance charge‐carrier mobility up to 0.55 cm² V^?1 s^?1. The outstanding charge‐transport characteristics of this polymer allowed the realization of high‐performance organic solar cells with a power conversion efficiency (PCE) of 5.1 %. Detailed studies on the morphological factors that enable the maximum PCE of the polymer solar cells are discussed along with a hole/electron mobility analysis based on the space‐charge‐limited current model.     

Complementary Hydrogen Bonding Modulates Electronic Properties and Controls Self‐Assembly of Donor/Acceptor Semiconductors

A comprehensive investigation of the complementary H‐bonding‐mediated self‐assembly between dipyrrolo[2,3‐b:3′,2′‐e]pyridine (P2P) electron donors and naphthalenediimide/perylenediimide (NDI/PDI) acceptors is reported. The synthesis of parent P2P and several aryl‐substituted derivatives is described, along with their optical, redox, and single‐crystal packing characteristics. The dual functionality of heteroatoms in the P2P/NDI(PDI) assembly, which act as proton donors/acceptors and also contribute to π‐conjugation, leads to H‐bonding‐induced perturbation of electronic levels. Concentration‐dependent NMR and UV/Vis spectroscopic studies revealed a cooperative effect of H‐bonding and π–π stacking interactions. This H‐bonding‐mediated co‐assembly of donor (D) and acceptor (A) components leads to a new charge‐transfer (CT) absorption that can be controlled throughout the visible range. The electronic interactions between D and A were further investigated by time‐dependent DFT, which provided insights into the nature of the CT transition. Electropolymerization of difuryl‐P2P afforded the first conjugated polymer incorporating H‐bonding recognition units in its main chain.     

Highly Segregated Lamello‐Columnar Mesophase Organizations and Fast Charge Carrier Mobility in New Discotic Donor–Acceptor Triads

Four new donor–acceptor triads (D–A–D) based on discotic and arylene mesogens have been synthesized by using Sonogashira coupling and cyclization reactions. This family of triads consists of two side‐on pending triphenylene mesogens, acting as the electron‐donating groups (D), laterally connected through short lipophilic spacers to a central perylenediimide (PI), benzo[ghi]perylenediimide (BI), or coronenediimide (CI) molecular unit, respectively, playing the role of the electron acceptor (A). All D–A–D triads self‐organize to form a lamello‐columnar oblique mesophase, with a highly segregated donor–acceptor (D–A) heterojunction organization, consequent to efficient molecular self‐sorting. The structure consists in the regular alternation of two disrupted rows of triphenylene columns and a continuous row of diimine species. High‐resolution STM images demonstrate that PI‐TP2 forms stable 2D self‐assembly nanostructures with some various degrees of regularity, whereas the other triads do not self‐organize into ordered architectures. The electron‐transport mobility of CI‐TP2, measured by time‐of‐flight at 200 °C in the mesophase, is one order of magnitude higher than the hole mobility. By means of this specific molecular designing idea, we realized and demonstrated for the first time the so‐called p–n heterojunction at the molecular level in which the electron‐rich triphenylene columns act as the hole transient pathways, and the coronenediimide stacks form the electron‐transport channels.     

Efficient Photoinduced Energy Transfer in a Newly Developed Hybrid SBA‐15 Photonic Antenna

A new hybrid photostable donor–acceptor mesoporous SBA‐15 silica system was designed and prepared. It consists of an encapsulated donor, the Super Yellow (SY) polymer, which transfers the photoexcitation energy directly to an acceptor dye that is linked outside the framework. The obtained composite material was characterized by X‐ray diffraction, nitrogen‐physisorption porosimetry, diffuse‐reflectance (DR)‐UV/Vis spectroscopy and photoluminescence, space‐ and time‐resolved confocal microscopy. The physico‐chemical analyses showed that the system behaves as an efficient Förster resonance energy transfer (FRET) pair, and high photoluminescence was observed from the acceptor. The presented photonic antenna is the first example of dye sensitization by polymer‐loaded mesoporous silica and represents a step forward in the search for new efficient and stable materials with opto‐electronic applications.     

HOMO Stabilisation in π‐Extended Dibenzotetrathiafulvalene Derivatives for Their Application in Organic Field‐Effect Transistors

Three new organic semiconductors, in which either two methoxy units are directly linked to a dibenzotetrathiafulvalene (DB‐TTF) central core and a 2,1,3‐chalcogendiazole is fused on the one side, or four methoxy groups are linked to the DB‐TTF, have been synthesised as active materials for organic field‐effect transistors (OFETs). Their electrochemical behaviour, electronic absorption and fluorescence emission as well as photoinduced intramolecular charge transfer were studied. The electron‐withdrawing 2,1,3‐chalcogendiazole unit significantly affects the electronic properties of these semiconductors, lowering both the HOMO and LUMO energy levels and hence increasing the stability of the semiconducting material. The solution‐processed single‐crystal transistors exhibit high performance with a hole mobility up to 0.04 cm² V^?1 s^?1 as well as good ambient stability.     

Diketopyrrolopyrrole?Thiophene‐Based Acceptor–Donor–Acceptor Conjugated Materials for High‐Performance Field‐Effect Transistors

We report the synthesis, morphology, and field‐effect‐transistor (FET) characteristics of new acceptor–donor–acceptor conjugated materials that consist of diketopyrrolopyrrole (DPP) acceptor groups and one of four different thiophene moieties, that is, dithiophene (2T), thieno[3,2‐b]‐thiophene (TT), dithieno[3,2‐b:2′,3′‐d]‐thiophene (DTT), and 5,5′′′‐di‐(2‐ethylhexyl)‐[2,3′;5′,2′′;4′′,2′′′]quaterthiophene (4T). The optical band gaps of the as‐prepared materials are smaller than 1.7 eV, which is attributed to the strong intramolecular charge transfer and the backbone coplanarity of the thiophene moieties. The order of both crystallinity and FET mobility (×10^?2–×10^?4 cm² V^?1 s^?1) is TT2DPP > 4T2DPP > 2T2DPP >DTT2DP, which differ in the structure of the π‐conjugated cores and core symmetry. Well‐ordered intermolecular chain packing was confirmed by the GIXD and AFM results. In particular, the FET hole mobility of TT2DPP was further improved to 0.1 cm² V^?1 s^?1, which was attributed to the well‐interconnected structure through solution‐shearing. These experimental results suggest the potential applications of the new DPP? thiophene? DPP conjugated materials for organic electronic devices.     

Photocatalytic Hydrogen Evolution Based on Efficient Energy and Electron Transfers in Donor–Bridge–Acceptor Multibranched‐Porphyrin‐Functionalized Platinum Nanocomposites

Two donor–bridge–acceptor conjugates (5,10,15,20‐tetrakis[4‐(N,N‐diphenylaminobenzoate)phenyl] porphyrin (TPPZ) and 5,10,15,20‐tetrakis[4‐(N,N‐diphenylaminostyryl)phenyl] porphyrin (TPPX)) were covalently linked to triphenylamine (TPA) at the meso‐position of porphyrin ring. The triphenylamine entities were expected to act as energy donors and the porphyrins to act as an energy acceptor. In this paper, we report on the synthesis of these multibranched‐porphyrin‐functionalized Pt nanocomposites. The conjugates used here not only served as a stabilizer to prevent agglomeration of Pt nanoparticles, but also as a light‐harvesting photosensitizer. The occurrence of photoinduced electron‐transfer processes was confirmed by time‐resolved fluorescence and photoelectrochemical spectral measurements. The different efficiencies for energy and electron transfer in the two multibranched porphyrins and the functionalized Pt nanocomposites were attributed to diverse covalent linkages. Moreover, in the reduction of water to produce H₂, the photocatalytic activity of the Pt nanocomposite functionalized by TPPX, in which the triphenylamine and porphyrin moieties are bonded through an ethylene bridge, was much higher than that of the platinum nanocomposite functionalized by TPPZ, in which the two moieties are bonded through an ester. This investigation demonstrates the fundamental advantages of constructing donor–bridge–acceptor conjugates as highly efficient photosensitizers based on efficient energy and electron transfer.     

A Bipolar Transporter as an Efficient Green Fluorescent Emitter and Host for Red Phosphors in Multi‐ and Single‐Layer Organic Light‐Emitting Diodes

Multifunctional donor–acceptor compound 4,4′‐bis(dibenzothiophene‐S,S‐dioxide‐2‐yl)triphenylamine ( DSTPA ) was obtained by linking a strongly electron‐withdrawing core and a strongly electron‐donating core with a biphenyl bridge in linear spatial alignment. DSTPA not only has suitable HOMO and LUMO levels for easily accepting both holes and electrons, it was also demonstrated to have a high fluorescence quantum yield of 0.98 and a high triplet energy level of 2.39 eV. Versatile applications of DSTPA for bipolar transport, green fluorescent emission, and sensitizing a red phosphor were systematically investigated in a series of multi‐ and single‐layer organic light‐emitting devices. In traditional multilayer devices, it shows excellent performance both in an undoped fluorescent device (used as a green emitter and achieving maximum current and power efficiencies (CE and PE) of 12.6 cd A^?1 and 9.4 Lm W^?1, respectively) and in a red phosphorescent device (used as a host and achieving maximum CE and PE of 26.4 cd A^?1 and 26.3 Lm W^?1, respectively). Furthermore, DSTPA was also simultaneously used as an emitter, a hole transporter, and an electron transporter in a single‐layer device showing CE and PE of 5.1 cd A^?1 and 4.7 Lm W^?1, respectively. A single‐layer red phosphorescent device with efficiencies of 11.7 cd A^?1 and 12.6 Lm W^?1 was obtained by doping DSTPA with a red phosphor. The performances of all of the devices in this work are comparable to the best of their corresponding classes in the literature.     

Exploring the Electronic Structure of an Organic Semiconductor Based on a Compactly Fused Electron Donor–Acceptor Molecule

A Mott‐type semiconductor based on a compactly fused and partially oxidized electron donor–acceptor (D–A) molecule was recently prepared and identified to exhibit a large room‐temperature conductivity of 2 S cm^?1. In a marked contrast to the organic conductors characterized by relatively well decoupled and segregated uniform stacks of D and A moieties, the formally half‐oxidized tetrathiafulvalene donors of the actual compound are organized in columnar π stacks only, whereby the coplanar electron‐acceptor units, namely benzothiadiazole, are closely annulated along their ridges. Herein, we present a theoretical study that explores the electronic structure of this novel type of organic semiconductor. The highly symmetric‐solid state material behaves as a one‐dimensional electronic system with strong antiferromagnetic interactions (coupling constant>200 cm^?1). The unique shape and local dipole of this redox‐active fused electron D–A molecule lays the basis for further investigations of the collective electronic structure, mainly in the function of different counterions embedded in the crystalline lattice.     

A Periodic Mesoporous Organosilica‐Based Donor–Acceptor System for Photocatalytic Hydrogen Evolution

A new solid‐sate donor–acceptor system based on periodic mesoporous organosilica (PMO) has been constructed. Viologen (Vio) was covalently attached to the framework of a biphenyl (Bp)‐bridged PMO. The diffuse reflectance spectrum showed the formation of charge‐transfer (CT) complexes of Bp in the framework with Vio in the mesochannels. The transient absorption spectra upon excitation of the CT complexes displayed two absorption bands due to radical cations of Bp and Vio species, which indicated electron transfer from Bp to Vio. The absorption bands slowly decayed with a half‐decay period of approximately 10 μs but maintained the spectral shape, thereby suggesting persistent charge separation followed by recombination. To utilize the charge separation for photocatalysis, Vio–Bp–PMO was loaded with platinum and its photocatalytic performance was tested. The catalyst successfully evolved hydrogen with excitation of the CT complexes in the presence of a sacrificial agent. In contrast, reference catalysts without either Bp–PMO or Vio gave no or little hydrogen generation, respectively. In addition, a homogeneous solution system of Bp molecules, methylviologen, and colloidal platinum also evolved no hydrogen, possibly due to a weaker electron‐donating feature of molecular Bp than that of densely packed Bp in Bp–PMO. These results indicated that densely packed Bp and Vio are essential for hydrogen evolution in this system and demonstrated the potential of PMO as the basis for donor–acceptor systems suitable for photocatalysis.     

Quantum Mechanical and Experimental Validation that Cyclobis(paraquat‐p‐phenylene) Forms a 1:1 Inclusion Complex with Tetrathiafulvalene

The promiscuous encapsulation of π‐electron‐rich guests by the π‐electron‐deficient host, cyclobis(paraquat‐p‐phenylene) (CBPQT⁴⁺), involves the formation of 1:1 inclusion complexes. One of the most intensely investigated charge‐transfer (CT) bands, assumed to result from inclusion of a guest molecule inside the cavity of CBPQT⁴⁺, is an emerald‐green band associated with the complexation of tetrathiafulvalene (TTF) and its derivatives. This interpretation was called into question recently in this journal based on theoretical gas‐phase calculations that reinterpreted this CT band in terms of an intermolecular side‐on interaction of TTF with one of the bipyridinium (BIPY²⁺) units of CBPQT⁴⁺, rather than the encapsulation of TTF inside the cavity of CBPQT⁴⁺. We carried out DFT calculations, including solvation, that reveal conclusively that the CT band emerging upon mixing TTF with CBPQT⁴⁺ arises from the formation of a 1:1 inclusion complex. In support of this conclusion, we have performed additional experiments on a [2]rotaxane in which a TTF unit, located in the middle of its short dumbbell, is prevented sterically from interacting with either one of the two BIPY²⁺ units of a CBPQT⁴⁺ ring residing on a separate [2]rotaxane in a side‐on fashion. This [2]rotaxane has similar UV/Vis and ¹H NMR spectroscopic properties with those of 1:1 inclusion complexes of TTF and its derivatives with CBPQT⁴⁺. The [2]rotaxane exists as an equimolar mixture of cis‐ and trans‐isomers associated with the disubstituted TTF unit in its dumbbell component. Solid‐state structures were obtained for both isomers, validating the conclusion that the TTF unit, which gives rise to the CT band, resides inside CBPQT⁴⁺.     

Separation of Electrical and Optical Energy Gaps: Selectively Adjusting the Electrical and Optical Properties for a Highly Efficient Blue Emitter

The design concept of separation of optical and electrical bandgap for wide bandgap materials is further developed in DCzSiPI. The HOMO/LUMO levels can be tuned by incorporation of PI and DCz substituents. The tetraphenylsilane core avoids the intramolecular charge transfer from DCz to PI (DCz=dimer carbazole, PI=phenanthro[9,10‐d]imidazole). The allowed transitions are found to be from HOMO?1 to LUMO providing DCzSiPI with sufficient bandgap.     

Synthesis of 2‐Azulenyl‐1,1,4,4‐tetracyano‐3‐ferrocenyl‐1,3‐butadienes by [2+2] Cycloaddition of (Ferrocenylethynyl)azulenes with Tetracyanoethylene

1‐, 2‐, and 6‐(Ferrocenylethynyl)azulene derivatives 10 – 16 have been prepared by palladium‐catalyzed alkynylation of ethynylferrocene with the corresponding haloazulenes under Sonogashira–Hagihara conditions. Compounds 10 – 16 reacted with tetracyanoethylene (TCNE) in a [2+2] cycloaddition–cycloreversion reaction to afford the corresponding 2‐azulenyl‐1,1,4,4,‐tetracyano‐3‐ferrocenyl‐1,3‐butadiene chromophores 17 – 23 in excellent yields. The redox behavior of the novel azulene chromophores 17 – 23 was examined by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.