Synthesis of indano[60]fullerene thioketone and its application in organic solar cells.

Evaporable indano[60]fullerene ketone (FIDO) was converted to indano[60]fullerene thioketone (FIDS) in high yield by using Lawesson's reagent. Three compounds with different substituents in para position were successfully converted to the corresponding thioketones, showing that the reaction tolerates compounds with electron-donating and electron-withdrawing substituents. Computational studies with density functional theory revealed the unique vibrations of the thioketone group in FIDS. The molecular structure of FIDS was confirmed by single-crystal X-ray analysis. Bulk heterojunction organic solar cells using three evaporable fullerene derivatives (FIDO, FIDS, C60) as electron-acceptors were compared, and the open-circuit voltage with FIDS was 0.16 V higher than that with C60.

Ni/Co-Catalyzed Homo-Coupling of Alkyl Tosylates.

A direct reductive homo-coupling of alkyl tosylates has been developed by employing a combination of nickel and nucleophilic cobalt catalysts. A single-electron-transfer-type oxidative addition is a pivotal process in the well-established nickel-catalyzed coupling of alkyl halides. However, the method cannot be applied to the homo-coupling of ubiquitous alkyl tosylates due to the high-lying σ*(C-O) orbital of the tosylates. This paper describes a Ni/Co-catalyzed protocol for the activation of alkyl tosylates on the construction of alkyl dimers under mild conditions.

[A case of transverse colon cancer with idiopathic mesenteric phlebosclerosis].

A 74-year-old male was diagnosed with transverse colon carcinoma with idiopathic mesenteric phlebosclerosis (IMP). Extended right hemicolectomy with regional lymph node dissection was performed. It has been reported that IMP develops after taking Chinese herbs containing SANSIS for a long time. In this case, the patient had taken such an herb for more than 3 years. In Japan, total 6 cases have been reported on a tumor with IMP, including this case. Immunohistological examination showed that the IMP findings were particularly strong around the tumor. Thus, this case suggests that there is a link between the tumor and IMP.

Selective Synthesis and Properties of Electron-Deficient Hybrid Naphthalene-Based π-Conjugated Systems.

One driving force for advancing the field of semiconducting polymers is to create new π-conjugated systems as building units. This work reports on a series of electron-deficient hybrid naphthalene-based π-conjugated systems in which two different units among benzoxadiazole, benzothiadiazole, benzoselenadiazole, and benzopyrazine (quinoxaline) were fused. These π-conjugated systems were synthesized in excellent yields via the selective one-side ring-opening reaction of corresponding naphthobischalcogenadiazoles using the NaBH4 /CoCl2 reduction reagents, followed by the ring-closing reactions. The electronic structure of these π-conjugated systems was studied in comparison with their parent systems. Furthermore, thiadiazolonaphthoxadiazole was incorporated into the π-conjugated polymer backbone. The electronic structure, film structure, and photovoltaic properties of the polymer were studied as well.

Three-component coupling of aryl iodides, allenes, and aldehydes catalyzed by a Co/Cr-hybrid catalyst.

The cobalt/chromium-catalyzed three-component coupling of aryl iodides, allenes, and aldehydes has been developed to afford multi-substituted homoallylic alcohols in a diastereoselective manner. Control experiments for understanding the reaction mechanism reveal that the cobalt catalyst is involved in the oxidative addition and carbometalation steps in the reaction, whereas the chromium salt generates highly nucleophilic allylchromium intermediates from allylcobalt species, without the loss of stereochemical information, to allow the addition to aldehydes.

Dithienyl Acenedithiophenediones as New π-Extended Quinoidal Cores: Synthesis and Properties.

We have synthesized two isomeric pairs of benzo- and naphthodithiophenediones with two flanking thiophenes and characterized them by single-crystal X-ray analysis, cyclic voltammetry, steady-state optical electronic absorption and emission spectroscopies, transient absorption spectroscopy, and vibrational spectroscopies with in situ spectroelectrochemistry techniques, and then compared them with the thieno[3,2-b]thiophene-2,5-dione counterpart that we previously reported. The results show that the central acenedithiophenedione cores have quinoidal conjugation with closed-shell character. The π-extension of the quinoidal core raises (lowers) the HOMO (LUMO) energy levels of the triads, resulting in the drastic reduction of their energy gaps from approximately 2.0 eV to 1.1 eV. Owing to the electron-withdrawing nature of the carbonyl terminal group at the quinoidal core, the triads have low-lying LUMO energy levels ranging from -3.9 eV to -4.3 eV, and can be regarded as strong electron-acceptor building units. Interestingly, the pairs of structural isomers have similar electronic structures in both the neutral and charged states despite the different shapes (linear and angular) and/or symmetry (C2h and C2v ) of the acenedithiophenedione cores.

Very Small Bandgap π-Conjugated Polymers with Extended Thienoquinoids.

The introduction of quinoidal character to π-conjugated polymers is one of the effective approaches to reducing the bandgap. Here we synthesized new π-conjugated polymers (PBTD4T and PBDTD4T) incorporating thienoquinoids 2,2'-bithiophene-5,5'-dione (BTD) and benzo[1,2-b:4,5-b']dithiophene-2,6-dione (BDTD) as strong electron-deficient (acceptor) units. PBTD4T showed a deep LUMO energy level of -3.77 eV and a small bandgap of 1.28 eV, which are similar to those of the analog using thieno[3,2-b]thiophene-2,5-dione (TTD) (PTTD4T). PBDTD4T had a much deeper LUMO energy level of -4.04 eV and a significantly smaller bandgap of 0.88 eV compared to those of the other two polymers. Interestingly, PBDTD4T showed high transparency in the visible region. The very small bandgap of PBDTD4T can be rationalized by the enhanced contribution of the resonance backbone structure in which the p-benzoquinodimethane skeleton in the BDTD unit plays a crucial role. PBTD4T and PBDTD4T exhibited ambipolar charge transport with more balanced mobilities between the hole and the electron than PTTD4T. We believe that the very small bandgap, i.e., the high near-infrared activity, as well as the well-balanced ambipolar property of the π-conjugated polymers based on these units would be of particular interest in the fabrication of next-generation organic devices.

Implication of Fluorine Atom on Electronic Properties, Ordering Structures, and Photovoltaic Performance in Naphthobisthiadiazole-Based Semiconducting Polymers.

The development of semiconducting polymers is imperative to improve the performance of polymer-based solar cells (PSCs). In this study, new semiconducting polymers based on naphtho[1,2-c:5,6-c']bis[1,2,5]thiadiazole (NTz), PNTz4TF2 and PNTz4TF4, having 3,3'-difluoro-2,2'-bithiophene and 3,3',4,4'-tetrafluoro-2,2'-bithiophene, respectively, are designed and synthesized. These polymers possess a deeper HOMO energy level than their counterpart, PNTz4T, which results in higher open-circuit voltages in solar cells. This concequently reduces the photon energy loss that is one of the most important issues surrounding PSCs. The PNTz4TF4 cell exhibits up to 6.5% power conversion efficiency (PCE), whereas the PNTz4TF2 cell demonstrates outstanding device performance with as high as 10.5% PCE, which is quite high for PSCs. We further discuss the performances of the PSCs based on these polymers by correlating the charge generation and recombination dynamics with the polymer structure and ordering structure. We believe that the results provide new insights into the design of semiconducting polymers and that there is still much room for improvement of PSC efficiency.

Organic semiconductors based on [1]benzothieno[3,2-b][1]benzothiophene substructure.

The design, synthesis, and characterization of organic semiconductors applicable to organic electronic devices, such as organic field-effect transistors (OFETs) and organic photovoltaics (OPVs), had been one of the most important topics in materials chemistry in the past decade. Among the vast number of materials developed, much expectation had been placed on thienoacenes, which are rigid and planar structures formed by fusing thiophenes and other aromatic rings, as a promising candidate for organic semiconductors for high-performance OFETs. However, the thienoacenes examined as an active material in OFETs in the 1990s afforded OFETs with only moderate hole mobilities (approximately 0.1 cm(2) V(-1) s(-1)). We speculated that this was due to the sulfur atoms in the thienoacenes, which hardly contributed to the intermolecular orbital overlap in the solid state. On the other hand, we have focused on other types of thienoacenes, such as [1]benzothieno[3,2-b][1]benzothiophene (BTBT), which seem to have appropriate HOMO spatial distribution for effective intermolecular orbital overlap. In fact, BTBT derivatives and their related materials, including dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT), have turned out to be superior organic semiconductors, affording OFETs with very high mobilities. To illustrate some examples, we have developed 2,7-diphenyl BTBT (DPh-BTBT) that yields vapor-deposited OFETs having mobilities of up to 2.0 cm(2) V(-1) s(-1) under ambient conditions, highly soluble dialkyl-BTBTs (Cn-BTBTs) that afford solution-processed OFETs with mobilities higher than 1.0 cm(2) V(-1) s(-1), and DNTT and its derivatives that yield OFETs with even higher mobilities (>3.0 cm(2) V(-1) s(-1)) and stability under ambient conditions. Such high performances are rationalized by their solid-state electronic structures that are calculated based on their packing structures: the large intermolecular orbital overlap and the isotropic two-dimensional electronic structure are the key regardless of the molecular size and substituents on the BTBT and its related thienoacene cores. Along with the discovery of such attracting performances, versatile and practical methods for the synthesis of BTBT and its derivatives, and the π-extended derivatives including DNTT, dianthra[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DATT), and the thienoacenes with two thieno[3,2-b]thiophene moieties, have been developed. In addition, the materials have been recently utilized in sophisticated devices and circuits, including all-printed transistor arrays, flexible circuits on ultrathin plastic substrates, and biomedical applications, underscoring their promise as practical semiconductors for electronic device applications. These exciting results of the present BTBT-based materials are expected to open doors to new horizons of organic semiconductors in terms of practical application and the design and synthesis of far more superior materials.

Naphthodithiophenes: emerging building blocks for organic electronics.

Linear-fused naphthodithiophenes (NDTs) are emerging building blocks in the development of new semiconducting small molecules, oligomers, and polymers. The promising nature of NDT-based materials as organic semiconductors has been demonstrated by superior device characteristics in organic field-effect transistors (OFETs) and organic photovoltaics (OPVs) in the last few years. In particular, it is quite impressive that a power conversion efficiency as high as 8.2% has been achieved for a single-junction OPV cell consisting of NDT-based semiconducting polymers and a fullerene derivative in such a short period of time. Here, we provide an overview of recent synthetic evolutions in NDT chemistry and progress in NDT-based materials, especially conjugated oligomers and polymers and their applications to OFETs and OPVs.

On the role of local charge carrier mobility in the charge separation mechanism of organic photovoltaics.

Although the charge separation (CS) and transport processes that compete with geminate and non-geminate recombination are commonly regarded as the governing factors of organic photovoltaic (OPV) efficiency, the details of the CS mechanism remain largely unexplored. Here we provide a systematic investigation on the role of local charge carrier mobility in bulk heterojunction films of ten different low-bandgap polymers and polythiophene analogues blended with methanofullerene (PCBM). By correlating with the OPV performances, we demonstrated that the local mobility of the blend measured by time-resolved microwave conductivity is more important for the OPV output than those of the pure polymers. Furthermore, the results revealed two separate trends for crystalline and semi-crystalline polymers. This work offers guidance in the design of high-performance organic solar cells.

5, 10-linked naphthodithiophenes as the building block for semiconducting polymers.

We present new semiconducting polymers incorporating naphtho[1, 2-b:5, 6-b'] dithiophene (NDT3) and naphtho[2, 1-b:6, 5-b'] dithiophene (NDT4), which are linked at the naphthalene positions, in the polymer backbone. It is interesting that the trend in the ordering structure and thus charge transport properties are quite different from what were observed in the isomeric polymers where the NDT3 and NDT4 cores are linked at the thiophene α-positions. In the thiophene-linked NDT system, the NDT3-based polymer (PNDT3BT) gave the better ordering in thin films and thus the high charge carrier mobility compared to the NDT4-based polymer (PNDT4BT). In the meantime, in the naphthalene-linked NDT system, the NDT4-based polymer (PNDT4iBT) provided the superior properties. Considering that PNDT4iBT has relatively low highest occupied molecular orbital (HOMO) energy level (-5.2 eV) and moderately high mobilities in the order of 10-2 cm2 V-1 s-1, the NDT4 core, when linked at the naphthalene positions, can be a good building unit for the development of high-performance semiconducting polymers for both organic field-effect transistors and photovoltaic devices.

[A case of rapidly progressing treatment-resistant colorectal neuroendocrine carcinoma].

We performed primary lesion resection in a 48-year-old man diagnosed with sigmoid colon cancer showing multiple liver metastases and extensive lymph node metastases. Endocrine cell carcinoma was diagnosed from an excised specimen. In the early postoperative period, orbital metastases and thoracic spine metastasis were detected, while the multiple liver metastases and lymph node metastases worsened markedly. We administered radiotherapy for the orbital and thoracic spine metastases, but it was ineffective. Treatment with anticancer agents was also ineffective. The patient died 56 days after the operation.

On-top π-stacking of quasiplanar molecules in hole-transporting materials: inducing anisotropic carrier mobility in amorphous films.

Dimers of partially oxygen-bridged triarylamines were designed and synthesized as hole-transporting materials. X-ray structural analyses revealed that these compounds form on-top π-stacking aggregates in the crystalline state. TRMC measurements showed that high levels of anisotropic charge transport were induced in the direction of the π-stacking. Surprisingly, even in vacuum-deposited amorphous films, these compounds retained some of the face-on π-stacking, thus facilitating an out-of-plane carrier mobility.

Simple π-Conjugated Polymers Based on Bithiazole for Nonfullerene Organic Photovoltaics.

Thiazole, as a family of five-membered heteroaromatic rings, is an interesting building unit that can play a role in coplanarizing the backbone as well as deepening the HOMO energy level, which is beneficial for the design of π-conjugated polymers for the photoactive materials in organic photovoltaics (OPVs). Here, we designed and synthesized π-conjugated polymers with simple chemical structures, which consist of 2,2'-bithiazole or 5,5'-bithiazole and alkylthiophenes as the polymer backbone. In fact, the polymers can be easily synthesized in much fewer steps compared to the typical high-performance polymers based on fused heteroaromatic rings. Interestingly, PTN5 exhibited a markedly higher ordered structure than PTN2. This was likely ascribed to the more coplanar and rigid backbone of PTN5 than that of PTN2 originating in the effectively arranged S···N interaction. As a result, the nonfullerene photovoltaic cell based on PTN5 showed a PCE of 12.2%, which was much higher than the cell based on PTN2 (4.3%) and was high for the polymers consisting of only nonfused rings. These results demonstrate that thiazole-based polymers are promising photoactive materials for OPVs and emphasize the importance of careful molecular design utilizing noncovalent interactions.

Manipulating the functionality and structures of π-conjugated polymers utilizing intramolecular noncovalent interactions towards efficient organic photovoltaics.

Careful control of electronic properties, structural order, and solubility of π-conjugated polymers is central to the improvement of organic photovoltaic (OPV) performance. In this work, we designed and synthesized a series of naphthobisthiadiazole-quaterthiophene copolymers by systematically replacing the alkyl groups with ester groups and changing the position of the fluorine groups in the quaterthiophene moiety. These alterations lowered the HOMO and LUMO energy levels and systematically varied the combination of intramolecular noncovalent interactions such as O⋯S and F⋯S interactions in the backbone. More importantly, although the introduction of such noncovalent interactions often lowers the solubility owing to the interlocking of backbone linkages, we found that careful design of the noncovalent interactions afforded polymers with relatively high solubility and high crystallinity at the same time. As a result, the power conversion efficiency of OPV cells that used fullerene (PC61BM) and nonfullerene (Y12) as the acceptor was improved. Our work offers important information for the development of high-performance π-conjugated polymers for OPVs.

Naphthodithiophene-naphthobisthiadiazole copolymers for solar cells: alkylation drives the polymer backbone flat and promotes efficiency.

We show that rational functionalization of the naphthodithiophene core in copolymers based on naphthodithiophene and naphthobisthiadiazole improves the solubility without an alteration of the electronic structure. Surprisingly, the introduction of linear alkyl chains brings about a drastic change in polymer orientation into the face-on motif, which is beneficial for the charge transport in solar cells. As a result, the present polymers exhibit high power conversion efficiencies of up to ~8.2% in conventional single-junction solar cells.

Naphthodithiophenediimide (NDTI): synthesis, structure, and applications.

A straightforward synthesis of α,ß-unsubstituted and α-halogenated naphtho[2,3-b:6,7-b']dithiophenediimides (NDTIs) is described. Electrochemical and optical studies of N,N-dioctyl-NDTI demonstrate that the compound has a low-lying LUMO energy level (4.0 eV below the vacuum level) and a small HOMO-LUMO gap (~2.1 eV). With its interesting electronic and optical properties, in addition to its planar structure, NDTI is a promising building block for the development of novel π-functional materials. In fact, it afforded n-channel, p-channel, and ambipolar materials, depending on the molecular modification.

Consecutive thiophene-annulation approach to π-extended thienoacene-based organic semiconductors with [1]benzothieno[3,2-b][1]benzothiophene (BTBT) substructure.

We describe a new synthetic route to the [1]benzothieno[3,2-b][1]benzothiophene (BTBT) substructure featuring two consecutive thiophene-annulation reactions from o-ethynyl-thioanisole substrates and arylsulfenyl chloride reagents that can be easily derived from arylthiols. The method is particularly suitable for the synthesis of unsymmetrical derivatives, e.g., [1]benzothieno[3,2-b]naphtho[2,3-b]thiophene, [1]benzothieno[3,2-b]anthra[2,3-b]thiophene, and naphtho[3,2-b]thieno[3,2-b]anthra[2,3-b]thiophene, a selenium-containing derivative, [1]benzothieno[3,2-b][1]benzoselenophene. It also allows us to access largely π-extended derivatives with two BTBT substructures, e.g., bis[1]benzothieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene and bis[1]benzothieno[2,3-d:2',3'-d']naphtho[2,3-b:6,7-b']dithiophene (BBTNDT). It should be emphasized that these new BTBT derivatives are otherwise difficult to be synthesized. In addition, since various substrates and reagents, o-ethynyl-thioanisoles and arylthiols, respectively, can be combined, the method can be regarded as a versatile tool for the development of thienoacene-based organic semiconductors in this class. Among the newly synthesized materials, highly π-extended BBTNDT afforded very high mobility (>5 cm(2) V(-1) s(-1)) in its vapor-deposited organic field-effect transistors (OFETs), which is among the highest for unsubstituted acene- or thienoacenes-based organic semiconductors. In fact, the structural analyses of BBTNDT both in the single crystal and thin-film state indicated that an interactive two-dimensional molecular array is realized in the solid state, which rationalize the higher carrier mobility in the BBTNDT-based OFETs.

Dependence of Exciton Binding Energy on Bandgap of Organic Semiconductors.

Strongly bound excitons crucially affect the operation of organic optoelectronic devices. Nevertheless, precise experimental data on the exciton binding energy of organic semiconductors are lacking. In this study, we determine the exciton binding energy as the difference between the optical and transport bandgaps with a precision of 0.1 eV. In particular, electron affinities with a precision higher than 0.05 eV determined by low-energy inverse photoelectron spectroscopy allow us to determine the transport gap and the exciton binding energies with such high precision. Through a systematic comparison of a wide range of organic semiconductors, including 42 organic solar cell materials (15 nonfullerene acceptors, 4 fullerene acceptors, 13 low-bandgap polymers, 7 organic light-emitting diode materials, and 3 crystalline materials), we found that the exciton binding energy is one-quarter of the transport gap regardless of the materials. We interpret this unexpected relation from a hydrogen atom-like model, i.e., the quantized energy levels in a Coulomb potential between the positive and the negative charges.