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p-n heterojunctions are fundamental components for electronics and optoelectronics, including diodes, transistors, sensors, and solar cells. Over the past few decades, organic-inorganic p-n heterojunctions have garnered significant interest due to the diverse properties they exhibit, which are a result of the limitless combinations of organic molecules and inorganic materials. This review article concentrates on photoinduced charge separation and photocurrent generation at heterojunctions between two-dimensional layered materials and structurally well-defined organic small molecules. We highlight representative examples, including our work, and critically discuss their potential and perspectives.

Porphyrin dyes with π-extended structures, particularly those with aromatic fused designs, have garnered considerable attention as efficient sensitizers for dye-sensitized solar cells (DCCSs). However, their photovoltaic performance has often been limited due to high aggregation tendencies caused by strong π-π interactions and charge recombination processes. Since m -terphenyls can be used as effective sterically protecting groups, the incorporation of umbrella-shaped m -terphenyls on the top of porphyrin dyes could provide an effective approach to unlock the full potential of highly π-extended porphyrin dyes. In this study, we report new fused porphyrin dyes, T-Ph , T- t BuPh , TT-Ph , and TT- t BuPh , introducing m -terphenyl groups. This innovative design ensures both blocking effects on dye aggregation on TiO 2 and charge recombination against redox shuttles. Under the optimized conditions, DSSCs using thiophene-fused porphyrins T-Ph and T- t BuPh achieved a remarkable power conversion efficiency (PCE) of 11.5%. This is high compared to those with reference porphyrins, GY50 possessing steric hindrance due to the orthogonal orientation of a V-shaped diarylamino group to the porphyrin plane and DfZnP without the bulky umbrella-shaped m -terphenyl, demonstrating the proof of our concept. More importantly, the cosensitized DSSC using T- t BuPh and the complementary dye XY1B afforded the highest PCE of 12.3% ever reported for DSSCs with fused porphyrin dyes. This demonstrates that the "umbrella-shaped m -terphenyl" design is an attractive methodology for enhancing the photovoltaic performance of DSSCs with highly π-extended planar dyes, especially fused porphyrin dyes.

We have reported that upon visible light irradiation, ferrocene-porphyrin-[60]fullerene triad molecules yield long-lived charge-separated states, enabling the control of the plasma membrane potential ( V m ) in living cells. These previous studies indicated that the localization of the triad molecules in a specific intra-membrane orientation and the suppression of the photodynamic actions of the [60]fullerene (C 60 ) moiety are likely important to achieve fast and safe control of V m , respectively. In this study, by mimicking our previous system of triad molecules and living cells, we report a simplified model system with a cationic C 60 derivative (catC 60 ) and a liposome with embedded 1-pyrenebutyric acid (PyBA) to demonstrate that the addition of PyBA was important to achieve fast and safer control of V m ., (Copyright © 2024, Takagi et al.)

Molecular donor-acceptor (D-A) linked systems have attracted significant attention due to their potential to address D-A interactions in excited states. In these systems, it is crucial to understand the interplay between electrons and spin behaviors, atomic nucleus movements (including vibration, rotation, fluctuation, and transfer), and collective motion (electron-phonon coupling) over time. Through intentional manipulation of locally excited, charge-transfer excited, and charge-separated states, along with modulation of dynamic effects (enhancement or restraint), we expect to unlock the full potential of D-A systems for photofunctions in electronics, energy, healthcare, and functional materials. In this perspective, we present our recent examples of D-A linked systems and related ones that address the aforementioned issues as part of our "Dynamic Exciton" research project in Japan., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

The power conversion efficiency (PCE) of organic photovoltaics (OPVs) has reached more than 19% due to the rapid development of non-fullerene acceptors (NFAs). To compete with the PCEs (26%) of commercialized silicon-based inorganic photovoltaics, the drawback of OPVs should be minimized. This drawback is the intrinsic large loss of open-circuit voltage; however, a general approach to this issue remains elusive. Here, we report a discovery regarding highly efficient NFAs, specifically ITIC. We found that charge-transfer (CT) and charge dissociation (CD) can occur even in a neat ITIC film without the donor layer. This is surprising, as these processes were previously believed to take place exclusively at donor/acceptor heterojunctions. Femtosecond time-resolved visible to mid-infrared measurements revealed that in the neat ITIC layers, the intermolecular CT immediately proceeds after photoirradiation (<0.1 ps) to form weakly-bound excitons with a binding energy of 0.3 eV, which are further dissociated into free electrons and holes with a time-constant of 56 ps. Theoretical calculations indicate that stacking faults in ITIC ( i.e. , V-type molecular stacking) induce instantaneous intermolecular CT and CD in the neat ITIC layer. In contrast, J-type stacking does not support such CT and CD. This previously unknown pathway is triggered by the larger dipole moment change on the excited state generated at the lower symmetric V-type molecular stacking of ITIC. This is in sharp contrast with the need of sufficient energy offset for CT and CD at the donor-acceptor heterojunction, leading to the significant voltage loss in conventional OPVs. These results demonstrate that the rational molecular design of NFAs can increase the local dipole moment change on the excited state within the NFA layer. This finding paves the way for a groundbreaking route toward the commercialization of OPVs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In dye-sensitized solar cells (DSSCs), flat planar dyes (e. g., highly light-harvesting porphyrins and corroles) with multiple anchoring groups are known to adopt a horizontal orientation on TiO 2 through the multiple binding to TiO 2 . Due to the strong electronic coupling between the dye and TiO 2 , fast charge recombination between the oxidized dye and an electron in TiO 2 occurs, lowering the power conversion efficiency (η). To overcome this situation, an additional donor moiety can be placed on top of the planar dye on TiO 2 to slow down the undesirable charge recombination. Here we report the synthesis and photovoltaic properties of a triarylamine (TAA)-tethered gold(III) corrole (TAA-AuCor). The DSSC with TAA-AuCor using iodine redox shuttle exhibited the highest η-value among corrole-based DSSCs, which is much higher than that with the reference AuCor. The transient absorption spectroscopies clearly demonstrated that fast electron transfer from the TAA moiety to the corrole radical cation in TAA-AuCor competes with the undesirable charge recombination to generate long-lived charge separated state TAA⋅ + -Cor/TiO 2 ⋅ - efficiently. Consequently, the introduction of the TAA moiety enhanced the η-value remarkably, demonstrating the usefulness of our new concept to manipulate charge-separated states toward highly efficient DSSCs., (© 2024 Wiley-VCH GmbH.)

This study reports the synthesis of cyclobutene derivatives in good yields via the [2 + 2] cycloaddition between lithium ynolates and α,β-unsaturated carbonyls. The ynolates are generated from α,α,α-tribromomethyl ketones and tert- butyl lithium via a simple and novel method, which does not produce any harmful byproducts, such as lithium alkoxide, which induces a polymerization reaction with α,β-unsaturated carbonyls.

Precise engineering of excited-state interactions between an organic conjugated molecule and a two-dimensional semiconducting inorganic nanosheet, specifically the manipulation of charge-transfer excited (CTE) states, still remains a challenge for state-of-the-art photochemistry. Herein, we report a long-lived, highly emissive CTE state at structurally well-defined hetero-nanostructure interfaces of photoactive pyrene and two-dimensional MoS 2 nanosheets via an N -benzylsuccinimide bridge (Py-Bn-MoS 2 ). Spectroscopic measurements reveal that no charge-transfer state is formed in the ground state, but the locally-excited (LE) state of pyrene in Py-Bn-MoS 2 efficiently generates an unusual emissive CTE state. Theoretical studies elucidate the interaction of MoS 2 vacant orbitals with the pyrene LE state to form a CTE state that shows a distinct solvent dependence of the emission energy. This is the first example of organic-inorganic 2D hetero-nanostructures displaying mixed luminescence properties by an accurate design of the bridge structure, and therefore represents an important step in their applications for energy conversion and optoelectronic devices and sensors., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Graphene oxide (GO) with its unique two-dimensional structure offers an emerging platform for designing advanced gas separation membranes that allow for highly selective transport of hydrogen molecules. Nevertheless, further tuning of the interlayer spacing of GO laminates and its effect on membrane separation efficiency remains to be explored. Here, positively charged fullerene C 60 derivatives are electrostatically bonded to the surface of GO sheets in order to manipulate the interlayer spacing between GO nanolaminates. The as-prepared GO-C 60 membranes have a high H 2 permeance of 3370 GPU (gas permeance units) and an H 2 /CO 2 selectivity of 59. The gas separation selectivity is almost twice that of flat GO membranes because of the role of fullerene.

The stability of singly or multiply negatively charged π-conjugated organic compounds is greatly influenced by their electronic delocalization. Herein, we report a strategic methodology for isolation of a mysterious compound. The isolated compounds, a pyreno[4,5- b ]pyrrole monoanion and pyreno[4,5- b :9,10- b ']dipyrrole dianion, were highly stable under ambient conditions due to high delocalization of the negative charge over multiple electron deficient C[triple bond, length as m-dash]N groups and pyrene π-scaffolds and allowed purification by column chromatography. To our knowledge, this is the first report on TCNE type reductive condensation of malononitrile involving pyrene di- and tetraone and formation of pyrenopyrrole. All compounds were characterized by spectroscopic methods and X-ray crystallography. A UV-vis spectroscopic study shows an intense low energy absorption band with a large absorption coefficient ( ε )., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We synthesized thiophene-fused porphyrin dimers as effective π-extended helical chromophores. The porphyrin dimers exhibit a red-shifted absorption with the edge extending up to 1100 nm, implying strong electronic communication over the two porphyrin moieties through the thiophene-fused structure. Importantly, their racemic inversion barriers can be modulated by the central metal ions.

Interfacial electron transfer across perovskite-electron acceptor heterojunctions plays a significant role in the power-conversion efficiency of perovskite solar cells. Thus, electron donor-acceptor thin films of halide perovskite nanocrystals receive considerable attention. Nevertheless, understanding and optimizing distance- and thickness-dependent electron transfer in perovskite-electron acceptor heterojunctions are important. We reveal the distance-dependent and diffusion-controlled interfacial electron transfer across donor-acceptor heterojunction films formed by formamidinium or cesium lead bromide (FAPbBr 3 /CsPbBr 3 ) perovskite nanocrystals with TiO 2 /C 60 . Self-assembled nanocrystal films prepared from FAPbBr 3 show a longer photoluminescence lifetime than a solution, showing a long-range carrier migration. The acceptors quench the photoluminescence intensity but not the lifetime in a solution, revealing a static electron transfer. Conversely, the electron transfer in the films changes from dynamic to static by moving toward the donor-acceptor interface. While radiative recombination dominates the electron transfer at 800 μm or farther, the acceptors scavenge the photogenerated carriers within 100 μm. This research highlights the significance of interfacial electron transfer in perovskite films.

For polycyclic aromatics with heterole-fused structures, the orientation of fused heterole rings as well as the geometry of their fused structures has a large impact on the physicochemical properties. In this study, a series of isomers of thiophene-fused naphthodiphospholes was designed and synthesized. Systematic investigation unveiled the explicit impact of heterole-fused structures on their structural and electronic properties. The isomers with 1,2/5,6-fused structure display phosphorescence due to enhanced spin-orbit coupling, whereas the isomers with 2,3/6,7-fused structure exhibit intense fluorescence. The trans isomers exhibited 1D slip π-stacked arrangement. In contrast, the cis isomers displayed 2D herringbone structure or columnar structure with a cavity. Therefore, the precisely controlled fusion of heterole rings is a universal approach to uncover their intrinsic properties for versatile applications as organic functional materials., (© 2020 Wiley-VCH GmbH.)

Morphological control of C 60 fullerene using liquefied porphyrins ( 1 and 2 ) as the host matrices was explored. Slow evaporation of the solvent of the equimolar mixture of porphyrin and C 60 in toluene afforded the porphyrin/C 60 composite with a 3:1 molar ratio. The stoichiometric binding behaviors suggest that specific porphyrin-C 60 interactions operate the formation of the porphyrin/C 60 composites, as corroborated by spectroscopic and thermal properties, and glazing-incidence wide-angle X-ray diffraction. Under the bulk conditions, the conventional thermodynamic advantage of multiple binding cooperativity for molecular recognition is unlikely to explain the stoichiometric binding behaviors. Instead, we propose a size-matching effect on the porphyrin-C 60 interaction in the bulk porphyrin matrices, i.e., "supramolecular solvation". The glassy nature of the porphyrin matrices was transmitted to C 60 through the specific interaction, and the porphyrin/C 60 composites adopted glassy states at room temperature.

Near-infrared (NIR) light control of living cellular activities is a highly desired technique for living cell manipulation because of its advantage of high penetrability towards living tissue. In this study, (π-extended porphyrin)-fullerene linked molecules are designed and synthesized to achieve NIR light control of the membrane potential. A donor-(π-extended porphyrin)-acceptor linked molecule exhibited the formation of the charge-separated state with a relatively long lifetime (0.68 μs) and a moderate quantum yield (27-31%). The hydrophilic trimethylammonium-linked triad molecule successfully altered PC12 cells' membrane potential via photoinduced intramolecular charge separation.

Background/aims: Light-induced control of the cell membrane potential has enabled important advances in the study of biological processes involving the nervous system and muscle activity. The use of these light-induced modifications is expected in various medical applications, including the control of physiological responses and the recovery of lost functions by regulating nerve activity. In particular, charge-separating linkage molecules (Charge-Separation (CS) molecules) can depolarize cells by photoexcitation without genetic processing. However, the molecular mechanisms underlying cell membrane depolarization are unknown and have hindered its application. Here, we show that CS molecules localized in the cell membrane of PC12 cells using a high-density lipoprotein (HDL)-based drug carrier can excite the cells through a novel membrane current regulation mechanism by light irradiation., Methods: Membrane potential, channel activity, and membrane capacitance were measured by patch clamp method in rat adrenal gland pheochromocytoma (PC12) cells and K V -overexpressing PC12 cells. CS molecules localized in the cell membrane of PC12 cells using HDL-based drug carrier. The localization of CS molecule was measured by a confocal microscopy. The mRNA expression was tested by RT-PCR., Results: Current clamp measurements revealed that the photo-activated CS molecule causes a sharp depolarization of about 15 mV. Furthermore, it was shown by voltage clamp measurement that this mechanism inactivates the voltage-dependent potassium current and simultaneously generates photo-activated CS molecule induced (PACS) current owing to the loss of the cell membrane capacitance. This activity continues the depolarization of the target cell, but is reversible via a regenerative mechanism such as endocytosis and exocytosis because the cell membrane is intact., Conclusion: Thus, the mechanism of photo-induced depolarization concludes that photo-activated TC1 causes depolarization by generating PACS current in parallel with the suppression of the K + current. Moreover, the depolarization slowly restores by internalization of TC1 from the membrane and insertion of new lipids into the cell membrane, resulting in the restoration of K V to normal activity and eliminating PACS currents, without cell damage. These results suggest the possibility of medical application that can safely control membrane excitation., Competing Interests: The authors have no conflicts of interest to declare., (© Copyright by the Author(s). Published by Cell Physiol Biochem Press.)

Porphyrins with a fused five-membered ring, such as 7,8-dehydropurpurins, have appeared as an emerging class of unique porphyrinoids. Their altered absorption spectra, relatively short lifetimes of excited states, and small HOMO-LUMO gaps arise from the harmony of the antiaromatic 20π-circuit and the aromatic 18π-circuit. In this regard, the electronic properties of 7,8-dehydropurpurins are expected to be controlled by modulating the contribution of the antiaromatic π-circuit to the whole aromaticity. Here the comparison of pyrrole- and phosphole-fused 7,8-dehydropurpurins is reported in terms of their aromaticity and physicochemical properties. The spectroscopic investigation revealed the larger contribution of the antiaromatic 24π-circuit in pyrrole-fused 7,8-dehyrdopurpurins than in phosphole-fused 7,8-dehydropurpurins. The DFT calculations also supported the feasibility of tuning the aromaticity of 7,8-dehydropurpurins by heterole-fused structures. Thus, the introduction of heterole-fused structures into porphyrinoids is a universal strategy to get new insight into aromaticity and their intrinsic properties in cyclic π-conjugated molecules., (© 2020 Wiley-VCH GmbH.)

Phase-separated structures in photoactive layers composed of electron donors and acceptors in organic photovoltaics (OPVs) generally exert a profound impact on the device performance. In this study, nonfullerene acceptors (NFAs) where a heteronanographene central core was furnished with branched alkoxy chains of different lengths, TACIC-EH, TACIC-BO, and TACIC-HD, were prepared to adjust the aggregation tendency and systematically probe the relationships of film structures with photophysical and photovoltaic properties. The side-chain length showed negligible effects on the absorption properties and energy levels of TACICs. In addition, regardless of the chain length, all TACIC films exhibited characteristically long singlet exciton lifetimes (1330-2330 ps) compared to those in solution (≤220 ps). Using a conjugated polymer donor, PBDB-T, the best OPV performance was achieved with TACIC-BO that contained medium-length chains, exhibiting a power conversion efficiency (PCE) of 9.92%. TACIC-HD with the longest chains showed deteriorated electron mobility due to the long insulating alkoxy groups. Therefore, the PBDB-T:TACIC-HD-based device revealed a low charge collection efficiency and PCE (8.21%) relative to the PBDB-T:TACIC-BO-based device, but their film morphologies were analogous. Meanwhile, TACIC-EH with the shortest chains showed low solubility and formed micrometer-sized large aggregates in the blend film with PBDB-T. Although the charge collection efficiency of PBDB-T:TACIC-EH was lower than that of PBDB-T:TACIC-BO, the efficiencies of exciton diffusion to the donor-acceptor interface were sufficiently high (>98%) owing to the elongated singlet exciton lifetime of TACIC-EH. The PCE of the PBDB-T:TACIC-EH-based device remained moderate (7.10%). Therefore, TACICs with the long singlet exciton lifetimes in the films provide a clear guideline for NFAs with low sensitivity of OPV device performance to the blend film structures, which is advantageous for large-scale OPV production with high reproducibility.

Few-layered antimonene (FLSb) nanosheets were noncovalently functionalized with fullerene C 60 clusters by quick addition of a poor solvent (i.e., acetonitrile) into a mixed dispersion of FLSb and C 60 in a good solvent (i.e., toluene). In a flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurement, the FLSb-C 60 composite, (FLSb+C 60 ) m , showed a rapid rise in transient conductivity, whereas no conductivity signal was observed in the single components, FLSb and C 60 . This demonstrated the occurrence of photoinduced charge separation between FLSb and C 60 in (FLSb+C 60 ) m . Furthermore, a photoelectrochemical device with an electrophoretically deposited (FLSb+C 60 ) m film exhibited an enhanced efficiency of photocurrent generation, compared to those of the single-components, FLSb and C 60 , due to the photoinduced charge separation between FLSb and C 60 . This work provides a promising approach for fabrication of antimonene-organic molecule composites and paves the way for their application in optoelectronics., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Compositional engineering has been a strong tool to improve the quality of the perovskite materials and, in turn, the reproducibility of the solar cells. However, the control over the active layer uniformity, one of the most important requirements for the obtainment of efficient devices, is still a weak point of perovskite solar cells (PSCs) manufacturing. Here, we develop an approach to grow a uniform mixed cation perovskite layer, foreseeing its implementation in inverted solar cells endowing organic transporting layers, through the addition of a stoiochiometric amount of tropolone as chelating agent for the lead. Thanks to low melting and boiling temperatures, tropolone is present in the system only during the colloidal liquid phase, leaving the film during its formation; this unique characteristic promotes the obtainment of ideal perovskite surface morphologies and an increased short circuit current of photovoltaic devices. A maximum power conversion efficiency of 20% was obtained, with a 25% increase with respect to the reference.

Electron-acceptor small-molecules possessing a long exciton lifetime and a narrow energy band gap, opposing the energy gap law, are highly desirable for high-performance organic photovoltaics (OPVs) by realizing their efficient light-harvesting ability (LH), exciton diffusion (ED), and charge transfer (CT). Toward this goal, we designed an acceptor-donor-acceptor (A-D-A) type nonfullerene acceptor (NFA), TACIC, having an electron-donating, self-assembling two-dimensional (2D) nanographene unit, thienoazacoronene, at the center with electron-withdrawing groups at both ends. The TACIC film exhibited a narrow band gap (1.59 eV) with excellent LH. Surprisingly, the TACIC film showed an extremely long exciton lifetime (1.59 ns), suppressing undesirable nonradiative decay by its unique self-assembling behavior. When combined with a conjugated polymer donor, PBDB-T, slow ED and CT were observed (60 ps) with the excitation of TACIC owing to the large TACIC domain sizes. Nevertheless, the unusually high efficiencies of ED and CT (96% in total) were achieved by the long TACIC exciton lifetime. Additionally, unusual energy transfer (EnT) from the excited PBDB-T to TACIC was seen, demonstrating its dual LH role. The OPV device with PBDB-T and TACIC showed a high incident photon-to-current efficiency (IPCE) exceeding 70% at up to 710 nm and a power conversion efficiency of ∼10%. This result will open up avenues for a rational strategy of OPVs where LH, ED, and CT from the acceptor side as well as LH, EnT, ED, and CT from the donor side can be better designed by using 2D nanographene as a promising building block for high-performance A-D-A type NFAs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In recent years, copper(I/II) complexes have emerged as alternative redox shuttles in dye-sensitized solar cells (DSSCs), exhibiting more positive redox potential than iodine- and cobalt-based redox shuttles. In particular, copper(I/II) complexes with 1,10-phenanthroline- or 2,2'-bipyridyl-based ligands attained moderate to high power conversion efficiencies (6-11%) with a high open-circuit voltage ( V OC ) over 1.0 V due to the positive potentials. Although copper(I/II) complexes with 1,10-phenanthroline-based ligands with 2,9-substituents have been developed, the effect of their ligand structures on the photovoltaic performance of DSSCs have not been fully addressed due to limited synthetic access to 1,10-phenanthroline derivatives. In this study, we designed and synthesized a series of copper(I/II) complexes with 1,10-phenanthroline ligands with different substituents at the 2,9-positions: bis(2- n -butyl-1,10-phenanthroline)copper(I/II) ([Cu(bp) 2 ] 1+/2+ ), bis(2-ethyl-9-methyl-1,10-phenanthroline)copper(I/II) ([Cu(emp) 2 ] 1+/2+ ), bis(2,9-diethyl-1,10-phenanthroline)copper(I/II) ([Cu(dep) 2 ] 1+/2+ ), and bis(2,9-diphenyl-1,10-phenanthroline)copper(I/II) ([Cu(dpp) 2 ] 1+/2+ ). The more positive redox potentials of [Cu(emp) 2 ] 1+/2+ and [Cu(dep) 2 ] 1+/2+ , compared to that of bis(2,9-dimethyl-1,10-phenanthroline)copper(I/II) ([Cu(dmp) 2 ] 1+/2+ ), originate from the larger steric hindrance of the ethyl group instead of the methyl group, whereas the redox potential of [Cu(bp) 2 ] 1+/2+ is significantly shifted to the negative direction because of the lower steric hindrance of the 2-monosubstituted 1,10-phenanthroline ligands. The efficiency of the DSSC with [Cu(bp) 2 ] 1+/2+ (5.90%) is almost comparable to the DSSC with [Cu(dmp) 2 ] 1+/2+ (6.29%). In contrast, the DSSCs with [Cu(emp) 2 ] 1+/2+ (3.25%), [Cu(dep) 2 ] 1+/2+ (2.56%), and [Cu(dpp) 2 ] 1+/2+ (2.21%) exhibited lower efficiencies than those with [Cu(dmp) 2 ] 1+/2+ and [Cu(bp) 2 ] 1+/2+ . The difference can be rationalized by the electron collection efficiencies. Considering the similar photovoltaic properties of the DSSCs with [Cu(bp) 2 ] 1+/2+ and [Cu(dmp) 2 ] 1+/2+ , the use of copper(I/II) complexes with 2-monosubstituted 1,10-phenanthroline ligands as the redox shuttle may be useful to improve the short-circuit current density while retaining the rather high V OC value when dyes with a smaller bandgap (i.e., better light harvesting) are developed.

Supramolecular composites composed of fullerene C 60 and carbon nanodiamond (ND) were constructed through spontaneous complexation of C 60 aggregates onto the surface of ND aggregates in N-methylpyrrolidone (NMP). The resulting C 60 -ND composite was assembled onto a nanostructured SnO 2 electrode by an electrophoretic deposition method. Formation of the C 60 -ND composite was confirmed by dynamic light scattering (DLS) and field-emission scanning electron microscopy (FESEM). The C 60 -ND composite on the SnO 2 electrode showed high incident photon-to-current efficiencies (IPCEs) in the visible region as compared with the single component system of C 60 or ND. The improved photocurrent generation of the C 60 -ND composite may result from the photoinduced charge separation at the interface between C 60 and ND. These results obtained here will provide valuable information on the design of optoelectronic devices based on all-nanocarbon materials., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Anchoring groups adopting a five-membered bidentate chelating are attractive to realize high power conversion efficiency (η) and long-term durability in dye-sensitized solar cells (DSSCs). In this regard, we chose catechol as an anchoring group that can adopt the chelating. However, the DSSCs with catechol-based sensitizers have never exceeded an η-value of 2 %. These poor photovoltaic performances may be associated with the electron-donating ability of the hydroxy groups in catechol. Considering these, we envisioned that fusing an electron-withdrawing thiazole moiety with a catechol anchoring group would improve its photovoltaic performance. Herein, we report a push-pull porphyrin sensitizer ZnPTC with a thiazolocatechol anchoring group. The DSSC with ZnPTC exhibited η=4.87 %. This value is the highest ever reported for catechol-anchor based DSSCs. Meanwhile, the long-term cell durability was not improved, although the robust anchoring properties were attained under harsh conditions., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Solar energy conversion is one of the most important issues for creating and maintaining a future sustainable society. In this regard, photovoltaic technologies have attracted much attention because of their potential to solve energy and environmental issues. In particular, thin-film solar cells, such as organic photovoltaics (OPVs) and perovskite solar cells (PSCs), are highly promising owing to their flexibility, light weight, and low-cost production. One of the most important factors used to evaluate solar-cell performance is the power conversion efficiency (PCE), which is the ratio of the output electric power divided by the input light power. The PCEs of PSCs have become comparable to those of multicrystalline silicon solar cells in a laboratory level, but the PCEs of OPVs have yet to catch up with them and still need to be improved. The insufficient durability of PSCs and OPVs is also a challenge that needs to be addressed. Fullerene derivatives have been utilized as electron acceptors and electron-transport materials in OPVs and PSCs. However, the use of fullerene derivatives requires attention to their isomers if they are multiadducts or even monoadducts produced from fullerenes with low symmetry. Their nonuniform structures and electronic properties may exert a negative effect on photovoltaic properties. However, most researchers in the field of OPVs and PSCs have been unaware of the importance of the isomerism. Even the most prevalent, high-performance fullerene acceptor, [6,6]-phenyl-C 71 -butyric acid methyl ester ([70]PCBM), has been used as an isomer mixture. In this Account, we summarize recent studies on the effects of isomer separation of fullerene derivatives on the device performances of OPVs and PSCs. Largely, fullerene derivatives containing various isomers are categorized into [60]fullerene bisadducts, [70]fullerene bisadducts, and [70]fullerene monoadducts. In all cases, the difference in isomerism was found to have a large impact on PCEs. The miscibility with polymer donors and film-forming property of fullerene derivatives were affected by the isomer separations, which exert the most potent influence on device performances. Although the disorders in energy levels among isomers are not definitely influencing on photovoltaic properties of isomer mixtures, the molecular packing structures of fullerene derivatives make a significant effect on their photovoltaic properties. Notably, isomerically pure fullerene derivatives often-but not always-exhibit higher PCEs than the isomer mixture. The search for the best isomers of fullerene derivatives and their optimal compositional ratios, which extensively depend on their roles and the combined materials, will be an indispensable step to achieving consistently higher device performances for OPVs and PSCs.

Photoconductivity is a characteristic property of semi-conductors. Herein, we present a photo-conducting crystalline metal-organic framework (MOF) thin film with an on-off photocurrent ratio of two orders of magnitude. These oriented, surface-mounted MOF thin films (SURMOFs), contain porphyrin in the framework backbone and C 60 guests, loaded in the pores using a layer-by-layer process. By comparison with results obtained for reference MOF structures and based on DFT calculations, we conclude that donor-acceptor interactions between the porphyrin of the host MOF and the C 60 guests give rise to a rapid charge separation. Subsequently, holes and electrons are transported through separate channels formed by porphyrin and by C 60 , respectively. The ability to tune the properties and energy levels of the porphyrin and fullerene, along with the controlled organization of donor-acceptor pairs in this regular framework offers potential to increase the photoconduction on-off ratio., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Over the last decades, porphyrin sensitizers have made a remarkable contribution to performance improvement in dye-sensitized solar cells (DSSCs). In particular, versatile push-pull-type porphyrin sensitizers have achieved power conversion efficiencies (η) over 10% as a result of their improved light-harvesting abilities. Meanwhile, aromatic ring fusion to a porphyrin core is an attractive option for highly efficient DSSCs because of its expanded π-conjugation and resultant red-shifted absorption. Nevertheless, aromatic-fused porphyrin sensitizers have suffered rather low cell performances due to their mismatch of HOMO-LUMO levels, high aggregation tendency, and short lifetime of the excited states. Bearing these in mind, we envisioned that the fusion of substituted methylene-bridged small aromatic ring to a porphyrin core would overcome these drawbacks, boosting the cell performance. Herein, we report a series of substituted methylene-bridged thiophene-fused porphyrins, AfZnP, DfZnP, and DfZnP- iPr. After optimization, DSSC with the donor-side thiophene-fused DfZnP- iPr achieved an η-value of 10.1%, which is comparable to that of DSSC with GY50 (10.0%), a representative high-performance push-pull-type porphyrin sensitizer. More importantly, cosensitization of DfZnP- iPr with a complementary sensitizer LEG4 further led to an η-value of 10.7%, which is the highest value ever reported for DSSCs with fused porphyrin sensitizers. Therefore, our strategy will reboot the exploration of aromatic-fused porphyrin sensitizers for high-performance DSSCs.

As structure defined cutouts of the graphene lattice, nanographene molecules have gained plenty of attention because of their high potential for versatile applications in organic electronics and energy conversion devices and as ideal model systems for the better understanding of intrinsic structure-property correlations of graphenes. In this study, well-defined nanographenes with sp 2 carbon networks of different sizes, hexa- peri -hexabenzocoronene (HBC) and its rectangularly π-extended version, a short graphene nanoribbon (GNR), have been covalently functionalized with photoactive porphyrin molecules. On the basis of their spectroscopic studies, the photodynamics of the porphyrin-linked nanographenes was found to be influenced substantially by the size of the nanographenes. Photoexcitation of the porphyrin-HBC linked system led to exclusive energy transfer (EnT) from the first singlet excited state (S 1 ) of the nanographene to the porphyrin, whereas opposite selective EnT occurred from the first and second singlet excited states (S 1 and S 2 ) of the porphyrin to the nanographene in the porphyrin-GNR linked system. In particular, ultrafast efficient EnTs from both the S 2 and S 1 states of the porphyrin to GNR mimic the corresponding ultrafast EnTs from the S 2 and S 1 states of carotenoids to chlorophylls in light-harvesting systems of natural photosynthesis. Such unique photophysical properties will be useful for the rational design of carbon-based photofunctional nanomaterials for optoelectronics and solar energy conversion devices.

Linear ladder-type π-conjugated molecules have attracted much interest because of their intriguing physicochemical properties. To modulate their electronic structures, an effective strategy is to incorporate main-group elements into ladder-type π-conjugated molecules. In line with this strategy, a variety of ladder-type π-conjugated molecules with main-group elements have been synthesized to explore their potential utility as organic functional materials. In this context, phosphole-based π-conjugated molecules are highly attractive, owing to their unique optical and electrochemical properties, which arise from the phosphorus atom. Herein, the synthesis and physicochemical properties of doubly thiophene-fused benzodiphospholes, as a new class of phosphole-based ladder-type π-conjugated molecule, are reported. Systematic investigations into the physicochemical properties of doubly thiophene-fused benzodiphospholes revealed their pluripotent features: intense near-infrared fluorescence, excellent two-photon absorption property, and remarkably high electron-transporting ability. This study demonstrates the potential utility of doubly thiophene-fused benzodiphospholes as organic functional materials for biological imaging, nonlinear optics, organic transistors, and organic photovoltaics., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Covalently linked porphyrin oligomers are attractive because of their extended π-conjugated systems. Among various porphyrin oligomers, directly meso-meso linked porphyrin oligomers exhibit unique photophysical properties due to their strong exciton couplings derived from the alternative orthogonal geometry of the porphyrins. Although their structural and electronic properties can be greatly altered by substituents at meso positions, it is still difficult to introduce different substituents at the meso positions. Thus, it is a challenge to develop general synthetic methodologies for functional porphyrin dimers and oligomers with different substituents at the meso positions. Herein, a general synthetic strategy for ABC-ABC-type directly meso-meso linked porphyrin dimers by stepwise functionalization starting from 10,15,20-meso-free 5-substituted porphyrin as building block is established. A meso-ABC-ABC-type meso-meso-linked donor-π-acceptor-type porphyrin dimer was prepared and exhibited the highest power conversion efficiency (7.91 %) ever reported for dye-sensitized solar cells based on dimeric orthogonal donor-π-acceptor-type organic sensitizers. This synthetic strategy will provide useful guidance for the rational design of functional porphyrin dimers and oligomers for diverse applications., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Perovskite and textured silicon solar cells were integrated into a tandem solar cell through a stacking method. To consider the effective structure of silicon solar cells for perovskite/silicon tandem solar cells, the optic and photovoltaic properties of textured and flat silicon surfaces were compared using mechanical-stacking-tandem of two- and four-terminal structures by perovskite layers on crystal silicon wafers. The reflectance of the texture silicon surface in the range of 750-1050 nm could be reduced more than that of the flat silicon surface (from 2.7 to 0.8%), which resulted in increases in average incident photon to current conversion efficiency values (from 83.0 to 88.0%) and current density (from 13.7 to 14.8 mA/cm 2 ). Using the texture surface of silicon heterojunction (SHJ) solar cells, the significant conversion efficiency of 21.4% was achieved by four-terminal device, which was an increase of 2.4% from that of SHJ solar cells alone.

The concept of chemical topology has generated considerable interest among chemists and one of the state-of-the-art topics is Möbius topology in cyclic π-conjugated molecules. In this regard, expanded porphyrins have been extensively studied because of their facile topological interconversions and attractive optoelectronic properties. A typical example involves [28]hexaphyrins: they show topological conversion between planar Hückel and twisted Möbius topologies owing to their flexible structure. With this in mind, we designed a [28]hexaphyrin where one dimethine pyrrole unit was replaced with dithieno[3,4- b :3',4'- d ]thiophene (β-DTT), aiming at a reversible switching between macrocyclic and cross-conjugated π-systems by a change in molecular topologies. Considering that the β-DTT unit can offer both macrocyclic and cross-conjugated π-circuits, we envisioned that a combination of the topological interconversion of [28]hexaphyrin with the two π-circuits of the β-DTT unit would enable a reversible switching between macrocyclic and cross-conjugated π-circuits on Möbius and Hückel topologies, respectively, by a simple conformational change. Unexpectedly, the hexaphyrin revealed a unique, unprecedented π-system switching between a Möbius cross-conjugated π-system and a Hückel antiaromatic π-system, which was fully supported by both experimental and theoretical investigations. Meanwhile, the [28]hexaphyrin was also found to be redox interconvertible with the corresponding [26]hexaphyrin with a Hückel cross-conjugated π-system. These results demonstrate that the β-DTT unit is a new effective motif to realize π-system switching by changing molecular and π-system topologies. Importantly, external stimuli, i.e. , solvent, as well as oxidation/reduction can be used to trigger the topological changes in expanded porphyrins with the help of the β-DTT unit.

In the past few decades, research on the construction of donor-bridge-acceptor linked systems capable of efficient photoinduced charge separation has fundamentally contributed to the fields of artificial photosynthesis and solar energy conversion. Specifically, the above systems are often fabricated by using carbon-based nanomaterials such as fullerenes, carbon nanotubes, and graphenes, offering limitless possibilities of tuning their optical and electronic properties. Accordingly, since understanding the structure-photodynamics relationships of π-aromatic donor-bridge-nanocarbon linked systems is crucial for extracting the full potential of nanocarbon materials, this review summarizes recent research on their photophysical properties featuring nanocarbon materials as electron acceptors. In particular, we highlight the electronic coupling effects on the photodynamics of donor-bridge-nanocarbon acceptor linked systems, together with the effects of donor dimerization. On a basis of their time-resolved spectroscopic data, the photodynamics of donor-bridge-nanocarbon acceptor linked systems is shown to be substantially influenced by the formation and decay of an exciplex state, i.e., an excited-state consisting of a π-molecular donor and a nanocarbon acceptor with partial charge-transfer character. Such basic information is essential for realizing future application of carbon-based nanomaterials in optoelectronic and energy conversion devices.

Fluoride (F - ) ion sensing is an important topic due to its roles in health, medical, and environmental sciences. In this regard, colorimetric sensors with a near infrared (NIR) optical response are useful in biological systems because they can avoid interference from endogenous chromophores. Although calix[n]phyrins are highly attractive as sensors with the NIR optical response, studies on calix[n]phyrins are still limited owing to their intrinsic instability against ambient light and air. In this study, we report the synthesis and characterization of a new calix[5]phyrin bearing one sp 3 -hybridized carbon atom as a π-expanded calix[n]phyrin. Upon addition of tetrabutylammonium fluoride, the calix[5]phyrin exhibited distinct NIR absorptions at 908 and 1064 nm as well as a visible color change. Importantly, it revealed an excellent selectivity for F - ion. These results demonstrate that calix[5]phyrins are promising colorimetric and NIR sensors of F - ion., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Carbon nanotubes (CNTs) interlocked by cyclic compounds through supramolecular interaction are promising rotaxane-like materials applicable as 2D and 3D networks of nanowires and disease-specific theranostic agents having multifunctionalities. Supramolecular complexation of CNTs with cyclic compounds in a "ring toss'' manner is a straightforward method to prepare interlocked CNTs; however, to date, this has not been reported on. Here, the "ring toss" method to prepare interlocked CNTs by using π-conjugated carbon nanorings: [8]-, [9]-, and [10]cycloparaphenyleneacetylene (CPPA) is reported. CPPAs efficiently interact with CNTs to form CNT@CPPA complexes, while uncomplexed CPPAs can be recovered without decomposition. CNTs, which tightly fit in the cavities of CPPAs through convex-concave interaction, efficiently afford "tube-in-ring"-type CNT@CPPA complexes. "Tube-in-ring"-type and "ring-on-tube"-type complexation modes are successfully distinguished by spectroscopic, thermogravimetric, and microscopic analyses., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Isomer-controlled [70]fullerene bis-adducts can achieve high performance as electron-acceptors in organic photovoltaics (OPVs) because of their stronger absorption intensities than [60]fullerene derivatives, higher LUMO energy levels than mono-adducts, and less structural and energetic disorder than random isomer mixtures. Especially, attractive are cis -1 isomers that have the closest proximity of addends owing to their plausible more regular close packed structure. In this study, propylene-tethered cis -1 bismethano[70]fullerene with two methyl, ethyl, phenyl, or thienyl groups were rationally designed and prepared for the first time to investigate the OPV performances with an amorphous conjugated polymer donor (PCDTBT). The cis -1 products were found to be a mixture of two regioisomers, α-1-α and α-1-β as major and minor components, respectively. Among them, the cis -1 product with two ethyl groups (Et 2 - cis -1-[70]PBC) showed the highest OPV performance, encouraging us to isolate its α-1-α isomer (Et 2 -α-1-α-[70]PBC) by high-performance liquid chromatography. OPV devices based on Et 2 - cis -1-[70]PBC and Et 2 -α-1-α-[70]PBC with PCDTBT showed open-circuit voltages of 0.844 V and 0.864 V, respectively, which were higher than that of a device with typical [70]fullerene mono-adduct, [70]PCBM (0.831 V) with a lower LUMO level. However, the short-circuit current densities and resultant power conversion efficiencies of the devices with Et 2 - cis -1-[70]PBC (9.24 mA cm -2 , 4.60%) and Et 2 -α-1-α-[70]PBC (6.35 mA cm -2 , 3.25%) were lower than those of the device with [70]PCBM (10.8 mA cm -2 , 5.8%) due to their inferior charge collection efficiencies. The results obtained here reveal that cis -1 [70]fullerene bis-adducts do not guarantee better OPV performance and that further optimization of the substituent structures is necessary., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We have synthesized dithieno[3,4- b:3',4'- d]phosphole derivatives as a new type of thiophene-fused phospholes. These dithienophospholes were found to show intramolecular charge transfer interactions by introducing electron-donating or -withdrawing groups on the peripheral aryl groups. Namely, they exhibit the unique hybrid character of electron-withdrawing phosphole and electron-donating thiophene.

Composite films that consisted of C 60 and well-exfoliated nanosheets of transition metal dichalcogenides (TMDs), such as MoS 2 or WS 2 , with a bulk heterojunction structure were easily fabricated onto a semiconducting SnO 2 electrode via a two-step methodology: self-assembly into their composite aggregates by injection of a poor solvent into a good solvent with the dispersion, and subsequent electrophoretic deposition. Upon photoexcitation, the composites on SnO 2 exhibited enhanced transient conductivity in comparison with single components of TMDs or C 60 , which demonstrates that the bulk heterojunction nanostructure of TMD and C 60 promoted the charge separation (CS). In addition, the decoration of the TMD nanosheets with C 60 hindered the undesirable charge recombination (CR) between an electron in SnO 2 and a hole in the TMD nanosheets. Owing to the accelerated CS and suppressed CR, photoelectrochemical devices based on the MoS 2 -C 60 and WS 2 -C 60 composites achieved remarkably improved incident photon-to-current efficiencies (IPCEs) as compared with the single-component films. Despite more suppressed CR in WS 2 -C 60 than MoS 2 -C 60 , the IPCE value of the device with WS 2 -C 60 was smaller than that with MoS 2 -C 60 owing to its inhomogeneous film structure., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The effects of regioisomer and diastereomer separations of [70]PCBM on structures and photovoltaic properties of PffBT4T-2OD:[70]PCBM blend films have systematically been investigated for the first time. Decreasing the amount of a diastereomer of β-[70]PCBM with high aggregation tendency (β 1 -[70]PCBM) improved the photovoltaic performances.

It has been known for decades that intracellular redox reactions control various vital functions in living systems, which include the synthesis of biomolecules, the modulation of protein functions, and cell signaling. Although there have been several reports on the control of such functions using DNA and RNA, the non-invasive optical control of biological functions is an important ongoing challenge. In this study, a hybrid of an electron donor-acceptor linked molecule based on a ferrocene(Fc)-porphyrin(ZnP)-fullerene(C 60 ) analogue and an elaborately designed nano-carrier, referred to herein as a MITO-Porter, resulted in a successful photoinduced intermolecular electron transfer reaction via the long-lived intramolecular charge separation, leading to site-specific reductive reactions in the mitochondria of living HeLa cells. A Fc-ZnP-C 60 linked molecule, 1-Oct, was designed and prepared for taking advantage of the unique photophysical properties with excellent efficiency (i.e. a long lifetime and a high quantum yield) for photoinduced charge separation. The targeted delivery of 1-Oct to mitochondria was accomplished by using a combination of the Fc-ZnP-C 60 molecule and a drug delivery nano-carrier, MITO-Porter, that was recently established by our group for intracellular cargo delivery. The successful delivery of 1-Oct by the MITO-Porter permitted the optically-controlled generation of O 2 - in the mitochondria of HeLa cells and the following induction of apoptosis as a cell signalling response was observed in confocal laser microscopy experiments. The obtained results indicate the use of an electron donor-acceptor system such as this can be a promising tool for the non-invasive triggering of redox-coupled cellular activities in living systems.

Donor-acceptor-linked molecules have been synthesized and utilized to induce the rapid and site-selective lipid-oxidation in mitochondria by utilizing a photoinduced intermolecular electron transfer reaction. Two water-soluble donor-acceptor molecules (1 and 2) were designed and synthesized for this purpose. 2 was prepared to modulate its affinity to cell membrane in mitochondria. Confocal laser microscopy experiments revealed that 1 and 2 possess high localization abilities in mitochondria. By the photoinduced electron transfer, 2 exhibited the remarkable oxidation ability of lipids, mainly cardiolipin. In HeLa cells, 2 triggered mitochondrial lipid oxidation, which was followed by apoptotic cell death, under illumination within a few seconds. These results show that the present molecular system is highly promising to utilize the photoinduced intermolecular electron transfer reaction in a precise spatiotemporal manner in a cell by using light.

Over the past several years, organometal halide perovskite solar cells (PSCs) have attracted considerable interest from the scientific research community because of their potential as promising photovoltaic devices for use in renewable energy production. To date, high power conversion efficiencies (PCEs) of more than 20% have been primarily achieved with mesoscopic-structured PSCs, where a mesoporous TiO 2 (mTiO 2 ) layer is incorporated as an electron-transporting mesoporous scaffold into the perovskite crystal, in addition to a compact TiO 2 (cTiO 2 ) as an electron-transporting layer (ETL). In this Perspective, we first summarize recent research on the preparation strategies of the mTiO 2 layer with a high electron transport capability by facile sol-gel methods instead of the conventional nanoparticle approach. The importance of the control of the pore size and grain boundaries of the mTiO 2 in achieving high PCEs for PSCs is discussed. In addition, an alternative method to improve the electron transport in the mTiO 2 layer via the incorporation of highly conductive nanocarbon materials, such as two-dimensional (2D) graphene and one-dimensional (1D) carbon nanotubes, is also summarized. Finally, we highlight the utilization of zero-dimensional (0D) nanocarbon, i.e., fullerenes, as an n-type semiconducting material in mesostructure-free planar PSCs, which avoids high-temperature sintering during the fabrication of an ETL.

Success of tumor photothermal immunotherapy requires a system that induces heat stress in cancer cells and enhances strong anti-tumor immune responses. Here, we designed a composite-type immunostimulatory DNA hydrogel consisting of a hexapod-like structured DNA (hexapodna) with CpG sequences and gold nanoparticles. Mixing of the properly designed hexapodna and oligodeoxynucleotide-modified gold nanoparticles resulted in the formation of composite-type gold nanoparticle-DNA hydrogels. Laser irradiation of the hydrogel resulted in the release of hexapodna, which efficiently stimulated immune cells to release proinflammatory cytokines. Then, EG7-OVA tumor-bearing mice received an intratumoral injection of a gold nanoparticle-DNA hydrogel, followed by laser irradiation at 780 nm. This treatment increased the local temperature and the mRNA expression of heat shock protein 70 in the tumor tissue, increased tumor-associated antigen-specific IgG levels in the serum, and induced tumor-associated antigen-specific interferon-γ production from splenocytes. Moreover, the treatment significantly retarded the tumor growth and extended the survival of the tumor-bearing mice., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Anchoring groups for dye-sensitized solar cells (DSSCs) play a decisive role in high-power conversion efficiency (η) and long-term cell durability. To date, a carboxylic acid is the most widely used anchoring group for DSSCs. However, the carboxylic acid tends to dissociate from a TiO 2 surface during the cell operation as well as in the presence of water. Considering that the dye dissociation from TiO 2 leads to a decrease in the cell performance, stable anchoring groups are highly desirable to achieve long-term durability of DSSCs toward their practical application. In this study, we designed and synthesized a series of porphyrin dyes with the triethoxysilyl anchoring groups, ZnPSi1 , ZnPSi2 , and ZnPSi3 , to evaluate the effects of the silicon-based anchoring group on cell durability and photovoltaic properties. The DSSCs based on ZnPSi1 , ZnPSi2 , and ZnPSi3 exhibited moderate η-values of 2.2, 4.7, and 2.3%, respectively. It is noteworthy that the η-value of the DSSC based on ZnPSi2 (4.7%) is the highest among DSSCs based on porphyrin dyes with silicon-based anchoring groups. The moderate η-values are mainly attributed to the low charge collection efficiency originating from the low surface coverage and plausible tilted geometry of the dyes on TiO 2 . More importantly, we demonstrated that the DSSC based on ZnPSi2 revealed higher long-term cell durability under illumination than that based on reference porphyrin YD2 -o -C8 having a conventional carboxylic acid anchoring group., Competing Interests: The authors declare no competing financial interest.

A hydroxamic acid group has been employed for the first time as an anchoring group for cobalt-based dye-sensitized solar cells (DSSCs). The porphyrin dye YD2-o-C8HA including a hydroxamic acid anchoring group exhibited a power conversion efficiency (η) of 6.4 %, which is close to that of YD2-o-C8, a representative porphyrin dye incorporating a conventional carboxylic acid. More importantly, YD2-o-C8HA was found to be superior to YD2-o-C8 in terms of both binding ability to TiO 2 and durability of cobalt-based DSSCs. Notably, YD2-o-C8HA photocells revealed a higher η-value (4.1 %) than YD2-o-C8 (2.8 %) after 500 h illumination. These results suggest that the hydroxamic acid can be used for DSSCs with other transition-metal-based redox shuttle to ensure high cell durability as well as excellent photovoltaic performance., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Light-inducible gene regulation has great potential for remote and noninvasive control of the fate and function of target cells. One method to achieve such control is delivery of heat shock protein (HSP) promoter-driven protein expression vectors and photothermal heaters into the cells, followed by activation by illumination. In this study, we show that gold nanorods (AuNRs) functionalized with two conventional lipids, oleate and 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP), are capable of efficient transfection and quick photoactivation of the HSP promoter. Use of our AuNRs (DOTAP-AuNRs) was comparable to Lipofectamine 2000 in terms of transfection efficiency, while lower in cytotoxicity. Subsequent near-infrared laser (NIR) illumination of the cells transfected by DOTAP-AuNRs for 10 s induced time- and site-specific transgene expression without significant phototoxicity, to a degree similar to that of heating the entire culture dish for 30 min. Our mechanistic studies suggest that efficient transfection and quick photoactivation of the HSP promoter (HSP70b') are due to the promoted endosomal escape of DOTAP-AuNRs. We propose a novel protocol for NIR-inducible, site-directed gene expression using an unprecedented complex of the three conventional components capable of both transfection and photothermal heating.

Two features of meso-Aryl-substituted expanded porphyrins suggest suitability as theranostic agents. They have excellent absorption in near infrared (NIR) region, and they offer the possibility of introduction of multiple fluorine atoms at structurally equivalent positions. Here, hexaphyrin (hexa) was synthesized from 2,6-bis(trifluoromethyl)-4-formyl benzoate and pyrrole and evaluated as a novel expanded porphyrin with the above features. Under NIR illumination hexa showed intense photothermal and weak photodynamic effects, which were most likely due to its low excited states, close to singlet oxygen. The sustained photothermal effect caused ablation of cancer cells more effectively than the photodynamic effect of indocyanine green (a clinical dye). In addition, hexa showed potential for use in the visualization of tumors by 19 F magnetic resonance imaging (MRI), because of the multiple fluorine atoms. Our results strongly support the utility of expanded porphyrins as theranostic agents in both photothermal therapy and 19 F MRI., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We synthesized for the first time octaphyrins with a dithieno[3,4-b:3',4'-d]thiophene core as thiophene-fused dithiaoctaphyrins with a cross-conjugated structure. The octaphyrins revealed cross-conjugated and macrocyclic 36π-electron networks.