Periodically Twisted Molecular Wires Based on a Fused Unit for Efficient Intramolecular Hopping Transport.

Realizing efficient long-distance intramolecular charge transport based on a hopping mechanism is a key challenge in molecular electronics. In hopping transport, a smaller reorganization energy (λ) and energy difference between hopping sites (ΔEhs) should lead to a smaller activation energy and faster charge transfer. However, the development of π-extended molecules that meet these requirements is challenging. In this study, we successfully synthesized several nanometer-scale π-extended molecules composed of a fused π-conjugated unit as a hopping site for reducing λ. Conformational twists between fused units effectively localize π-conjugation in each unit, contributing to reducing ΔEhs. The expected electronic structures of the oligomers were confirmed using spectroscopic and electrochemical measurements. Single-molecule conductance measurements exhibited higher conductance and lower activation energy than those of nonfused oligothiophenes. First-principles calculations indicated that smaller λ and ΔEhs values explain the high conductance. These results highlight the efficiency of the proposed molecular design for effective intramolecular hopping transport.

Nonfullerene Acceptors Bearing Spiro-Substituted Bithiophene Units in Organic Solar Cells: Tuning the Frontier Molecular Orbital Distribution to Reduce Exciton Binding Energy.

The development of nonfullerene acceptors (NFAs), represented by ITIC, has contributed to improving the power conversion efficiency (PCE) of organic solar cells (OSCs). Although tuning the electronic structures to reduce the exciton binding energy (Eb) is considered to promote photocharge generation, a rational molecular design for NFAs has not been established. In this study, we designed and developed two ITIC-based NFAs bearing spiro-substituted bithiophene or biphenyl units (named SpiroT-DCI and SpiroF-DCI) to tune the frontier molecular orbital (FMO) distribution of NFAs. While the highest occupied molecular orbitals (HOMOs) of SpiroF-DCI and ITIC are delocalized in the main π-conjugated framework, the HOMO of SpiroT-DCI is distributed on the bithiophene unit. Reflecting this difference, SpiroT-DCI exhibits a smaller Eb than either SpiroF-DCI or ITIC, and exhibits greater external quantum efficiency in single-component OSCs. Furthermore, SpiroT-DCI shows improved PCEs for bulk-heterojunction OSCs with a donor of PBDB-T, compared with that of either SpiroT-DCI or ITIC. Time-resolved spectroscopy measurements show that the photo-induced intermolecular charge separation is effective even in pristine SpiroT-DCI films. This study highlights the introduction of spiro-substituted bithiophene units that are effective in tuning the FMOs of ITIC, which is desirable for reducing the Eb and improving the PCE in OSCs.

A Dibenzo[g,p]chrysene-Based Organic Semiconductor with Small Exciton Binding Energy via Molecular Aggregation.

Exciton binding energy (Eb) is understood as the energy required to dissociate an exciton in free-charge carriers, and is known to be an important parameter in determining the performance of organic opto-electronic devices. However, the development of a molecular design to achieve a small level of Eb in the solid state continues to lag behind. Here, to investigate the relationship between aggregation and Eb, star-shaped π-conjugated compounds DBC-RD and TPE-RD were developed using dibenzo[g,p]chrysene (DBC) and tetraphenylethylene (TPE). Theoretical calculations and physical measurements in solution showed no apparent differences between DBC-RD and TPE-RD, indicating that these molecules possess similar properties on a single-molecule level.  By contrast, pristine films incorporating these molecules showed significantly different levels of electron affinity, ionization potential, and optical gap. Also, DBC-RD had a smaller Eb value of 0.24 eV compared with that of TPE-RD (0.42 eV). However, these molecules showed similar Eb values under dispersed conditions, which suggested that the decreased Eb of DBC-RD in pristine film is induced by molecular aggregation. By comparison with TPE-RD, DBC-RD showed superior performances in single-component organic solar cells and organic photocatalysts. These results indicate that a molecular design suitable for aggregation is important to decrease the Eb in films.

Colorless Near-Infrared Absorbing Dyes Based on B-N Fused Donor-Acceptor-Donor π-Conjugated Molecules for Organic Phototransistors.

The introduction of a colorless function to organic electronic devices allows responses to light in the near-infrared (NIR) region and is expected to broaden the applications of these devices. However, the development of a colorless NIR dye remains a challenge due to the lack of a rational molecular design for controlling electronic transitions. In this study, to suppress the π-π* transitions in the visible region, polycyclic donor-acceptor-donor π-conjugated molecules with boron bridges (Py-FNTz-B and IP-FNTz-B) are designed and synthesized, which contain pyrrole or indenopyrrole as donor units with fluorinated naphthobisthiadiazole (FNTz) as an acceptor unit. The pyrrole end-capped Py-FNTz-B shows an absorption band in the NIR region without distinct visible-light absorption, which has led to the establishment of colorless characteristics. The indenopyrrole end-capped IP-FNTz-B shows a narrow optical energy gap of 0.87 eV in films. Time-resolved microwave conductance and field-effect transistors demonstrate the semiconducting characteristics of these molecules, and Py-FNTz-B-based devices function as NIR phototransistors. Theoretical analyses indicate that the combination of a polyene-like electronic structure with orbital symmetry is important to obtain NIR wavelength-selective absorption. This study suggests that a molecular design based on electronic structures can be effective in the development of colorless NIR-absorbing dyes for organic electronics.

Invariant Charge Carrier Dynamics Using a Non-Planar Non-Fullerene Acceptor across Multiple Processing Solvents.

Conventional non-fullerene acceptors (NFAs) typically have planar structures that can enable improved electron mobility and produce more efficient organic photovoltaic devices. A relatively simple A-D-A'-D-A type NFA specifically designed to match with poly(3-hexylthiophene-2,5-diyl) (P3HT) for green-absorbing agrivoltaic applications has been examined using a variety of techniques: microsecond transient absorption spectroscopy, atomic force microscopy, and photoluminescence. Relatively invariant charge carrier decay dynamics are observed in the blend films across a variety of processing solvents. Raman spectroscopy in conjunction with computational studies reveals that this NFA is non-planar and that multiple conformations are present in films, while preserving the crystalline nature of P3HT. The non-planarity of the NFA therefore creates a dispersive acceptor environment, irrespective of processing solvent, and this leads to the observed relative invariance in charge carrier decay dynamics and high tolerance to morphological variation. The findings presented in this work highlight the potential of non-planar materials as acceptors in organic photovoltaic devices.

Single-Layer Organic Light-Emitting Diode with Trap-Free Host Beats Power Efficiency and Lifetime of Multilayer Devices.

Organic light-emitting diodes (OLEDs) employing a single active layer potentially offer a number of benefits compared to multilayer devices; reduced number of materials and deposition steps, potential for solution processing, and reduced operating voltage due to the absence of heterojunctions. However, for single-layer OLEDs to achieve efficiencies approaching those of multilayer devices, balanced charge transport is a prerequisite. This requirement excludes many efficient emitters based on thermally activated delayed fluorescence (TADF) that exhibit electron trapping, such as the green-emitting bis(4-(9,9-dimethylacridin-10(9H)-yl)phenyl)methanone (DMAC-BP). By employing a recently developed trap-free large band gap material as a host for DMAC-BP, nearly balanced charge transport is achieved. The single-layer OLED reaches an external quantum efficiency (EQE) of 19.6%, which is comparable to the reported EQEs of 18.9-21% for multilayer devices, but achieves a record power efficiency for DMAC-BP OLEDs of 82 lm W-1, clearly surpassing the reported multilayer power efficiencies of 52.9-59 lm W-1. In addition, the operational stability is greatly improved compared to multilayer devices and the use of conventional host materials in combination with DMAC-BP as an emitter. Next to the obvious reduction in production costs, single-layer OLEDs therefore also offer the advantage of reduced energy consumption and enhanced stability.

Green-light wavelength-selective organic solar cells for agrivoltaics: dependence of wavelength on photosynthetic rate.

There is a growing demand for the development of novel solar power systems that can simultaneously solve the problems associated with both energy generation and food supply in agriculture. Green-light wavelength-selective organic solar cells (OSCs), whose transmitted blue and red light can be utilized to promote plant growth were recently reported by our group. However, the influence of wavelength variation on the photosynthetic rate in green-light wavelength-selective OSCs remains unclear. In this study, we report on the design and synthesis of new electron-accepting π-conjugated molecules containing cyclopentene-annelated thiophene with a spiro-substituted 2,7-bis(2-ethylhexyl)fluorene (FT) unit (TT-FT-ID) as a green-light wavelength-selective nonfullerene acceptor along with a reference compound TT-T-ID. Photophysical measurements indicate that the introduction of the FT unit leads to an absorption band with a small full width at half maximum in films, leading to the ability to fine-tune the absorption length. Concerning the optimization of the conditions for the fabrication of the active layers, which are composed of a green-light wavelength-selective donor polymer of poly(3-hexylthiophene) (P3HT) and the new acceptors, Bayesian optimization based on Gaussian process regression was applied to minimize the experimental batches. The green-light wavelength-selective factor (SG) and the PCEs in the green-light region (PCE-GR) of the P3HT:TT-FT-ID-based device were determined to be 0.52 and 8.6%, respectively, which are higher values than those of the P3HT:TT-T-ID blend film. The P3HT:TT-FT-ID blend film increased the photosynthetic rate of green pepper compared to that of the P3HT:TT-T-ID blend film. These results indicate that the fine-tuning of the absorbance required for crop growth is an important issue in developing green-light wavelength-selective OSCs for agrivoltaics.

s-Indacene Revisited: Modular Synthesis and Modulation of Structures and Molecular Orbitals of Hexaaryl Derivatives.

Though s-indacene is an intriguing antiaromatic hydrocarbon of 12 π-electrons, it has been underrepresented due to the lack of efficient and versatile methods to prepare stable derivatives. Herein we report a concise and modular synthetic method for hexaaryl-s-indacene derivatives bearing electron-donating/-accepting groups at specific positions to furnish C2h-, D2h-, and C2v-symmetric substitution patterns. We also report the effects of substituents on their molecular structures, frontier molecular orbital (MO) levels, and magnetically induced ring current tropicities. Both theoretical calculations and X-ray structure analyses indicate that the derivatives of the C2h-substitution pattern adopt different C2h structures with significant bond length alternation depending on the electronic property of the substituents. Due to the nonuniform distribution of the frontier MOs, their energy levels are selectively modulated by the electron-donating substituents. This leads to the inversion of the HOMO and HOMO-1 sequences with respect to those of the intrinsic s-indacene as theoretically predicted and experimentally proven by the absorption spectra at visible and near-infrared regions. The NICS values and the 1H NMR chemical shifts of the s-indacene derivatives indicate their weak antiaromaticity. The different tropicities are explained by the modulation of the HOMO and HOMO-1 levels. In addition, for the hexaxylyl derivative, weak fluorescence from the S2 excited state was detected due to the large energy gap between the S1 and S2 states. Notably, an organic field-effect transistor (OFET) fabricated using the hexaxylyl derivative exhibited moderate hole carrier mobility, a result which opens the door for optoelectronic applications of s-indacene derivatives.

Fluorinated Dihydropentalene-1,4-Dione: A Strong Electron-Accepting Unit with Organic Semiconductor Characteristics.

Invited for the cover of this issue are Soichi Yokoyama and Yutaka Ie at Osaka University, Japan. The image depicts the strong electron affinity of the fluorinated dihydropentalene-1,4-dione (FPD) structure, in which the electron-rich amino groups in the diketopyrrolopyrrole (DPP) skeleton are replaced with a strongly electronegative difluoromethylene unit. Read the full text of the article at 10.1002/chem.202203873.

Correction: Phosphaacene as a structural analogue of thienoacenes for organic semiconductors.

Correction for 'Phosphaacene as a structural analogue of thienoacenes for organic semiconductors' by Kyohei Matsuo et al., Chem. Commun., 2022, 58, 13576-13579, https://doi.org/10.1039/D2CC05122B.

Fluorinated Dihydropentalene-1,4-Dione: A Strong Electron-Accepting Unit with Organic Semiconductor Characteristics.

The development of electron-accepting units is of significant importance because the construction of donor (D)-acceptor (A) configurations is an effective strategy for tuning the electronic properties of π-conjugated systems. Although doubly fused pentagons represented by diketopyrrolopyrrole (DPP) have been used as an effective electron-accepting unit, the relatively high-lying frontier molecular orbital levels (FMOs) leave room for further improvement. We report herein the synthesis of a fluorinated dihydropentalene-1,4-dione (FPD) derivative as a strong electron-accepting unit and the development of D-A-D π-extended molecules. X-ray analyses revealed that the presence of fluorine atoms contributed to the formation of high planar structures and slipped-stacked packing. Electrochemical measurements indicated that the FPD derivatives showed relatively lower FMO energy levels than the corresponding DPP-containing derivatives. The D-A-D molecule based on terthiophene and FPD showed semiconducting responses. This study demonstrates that the FPD unit can function as a new acceptor unit for organic semiconductors.

Phosphaacene as a structural analogue of thienoacenes for organic semiconductors.

An air-stable λ3-phosphinine-containing polycyclic aromatic compound without steric protection was synthesized and its charge transport properties were evaluated, which revealed moderate hole mobility. This research is the first experimental demonstration of the organic electronic applications of low-coordinate phosphorus compounds.

Tetrazolo[1,5-a]pyridine-Containing π-Conjugated Systems: Synthesis, Properties, and Semiconducting Characteristics.

The incorporation of an electron-accepting unit into π-conjugated systems is an important approach to modulate the physical properties of such molecules. To investigate the potential of tetrazolo[1,5-a]pyridine as an electron-accepting unit, a series of diarylated tetrazolo[1,5-a]pyridine derivatives was synthesized by treating the corresponding diarylated pyridine N-oxide with diphenylphosphoryl azide. Thermogravimetric analyses of these molecules indicated that they possessed good thermal stability. The bithiophene-substituted tetrazolo[1,5-a]pyridine compound showed stable transistor characteristics under repeated bias conditions.

Role of Linker Functionality in Polymers Exhibiting Main-Chain Thermally Activated Delayed Fluorescence.

Excellent performance has been reported for organic light-emitting diodes (OLEDs) based on small molecule emitters that exhibit thermally activated delayed fluorescence. However, the necessary vacuum processing makes the fabrication of large-area devices based on these emitters cumbersome and expensive. Here, the authors present high performance OLEDs, based on novel, TADF polymers that can be readily processed from a solution. These polymers are based on the acridine-benzophenone donor-acceptor motif as main-chain TADF chromophores, linked by various conjugated and non-conjugated spacer moieties. The authors' extensive spectroscopic and electronic analysis shows that in particular in case of alkyl spacers, the properties and performance of the monomeric TADF chromophores are virtually left unaffected by the polymerization. They present efficient solution-processed OLEDs based on these TADF polymers, diluted in oligostyrene as a host. The devices based on the alkyl spacer-based TADF polymers exhibit external quantum efficiencies (EQEs) ≈12%, without any outcoupling-enhancing measures. What's more, the EQE of these devices does not drop substantially upon diluting the polymer down to only ten weight percent of active material. In contrast, the EQE of devices based on the monomeric chromophore show significant losses upon dilution due to loss of charge percolation.

Dianion and Dication of Tetracyclopentatetraphenylene as Decoupled Annulene-within-an-Annulene Models.

The dianion and dication of tetramesityl-substituted tetracyclopentatetraphenylene, a circulene consisting of alternating five- and six-membered rings, have been generated by reduction with alkali metals and oxidation with antimony(V) halides, respectively. They are theoretically predicted to adopt double annulenoid structures called annulene-within-an-annulene models in which the outer and inner conjugation circuits are significantly decoupled. The theoretical structures were experimentally proven by X-ray crystallographic analyses and the electronic configurations were supported by MCD spectra. Based on the 13 C NMR chemical shifts, negative and positive charges are shown to be located mainly at the outer periphery, indicating that the dianion and dication have delocalized 22-π and 18-π electron outer perimeters, respectively, and 8-π electron structure at the inner ring. Notably, the dianion has an open-shell character, whereas the dication has a closed-shell ground state.

Excited states engineering enables efficient near-infrared lasing in nanographenes.

The spectral overlap between stimulated emission (SE) and absorption from dark states (i.e. charges and triplets) especially in the near-infrared (NIR), represents one of the most effective gain loss channels in organic semiconductors. Recently, bottom-up synthesis of atomically precise graphene nanostructures, or nanographenes (NGs), has opened a new route for the development of environmentally and chemically stable materials with optical gain properties. However, also in this case, the interplay between gain and absorption losses has hindered the attainment of efficient lasing action in the NIR. Here, we demonstrate that the introduction of two fluoranthene imide groups to the NG core leads to a more red-shifted emission than the precursor NG molecule (685 vs. 615 nm) and also with a larger Stokes shift (45 nm vs. 2 nm, 1026 cm-1vs. 53 cm-1, respectively). Photophysical results indicate that, besides the minimisation of ground state absorption losses, such substitution permits to suppress the detrimental excited state absorption in the NIR, which likely arises from a dark state with charge-transfer character and triplets. This has enabled NIR lasing (720 nm) from all-solution processed distributed feedback devices with one order of magnitude lower thresholds than those of previously reported NIR-emitting NGs. This study represents an advance in the field of NGs and, in general, organic semiconductor photonics, towards the development of cheap and stable NIR lasers.