Benzo[c]thiophene–C60 Diadduct: An Electron Acceptor for p–n Junction Organic Solar Cells Harvesting Visible to Near‐IR Light

We synthesized a new 56‐π‐electron fullerene derivative through a Diels–Alder cycloaddition of benzo[c]thiophene that featured a relatively low temperature, closer to stoichiometric use of the diene, and easy product purification. The 56‐π‐electron benzo[c]thiophene diadduct ( BTCDA ) has a LUMO energy level of 0.09 to 0.18 eV higher than that of 58‐π‐electron fullerenes, and therefore, the BTCDA ‐based organic photovoltaic device exhibited a higher open‐circuit voltage and power‐conversion efficiency (PCE). When used with a binary‐donor system, including visible‐light‐harvesting tetrabenzoporphyrin ( BP ) and near‐IR‐harvesting titanyl phthalocyanine ( TiOPc ), the device had a PCE that was 1.5–3 times higher (2.8 %) than that for devices with BP or TiOPc alone because the binary‐donor device can utilize light between λ=350 and 950 nm.     

Covalent Functionalization of Black Phosphorus with Conjugated Polymer for Information Storage

Major disadvantages of black phosphorus (BP) are its poor air‐stability and poor solubility in common organic solvents. The best way to solve this problem is to incorporate BP into a polymer backbone or a polymer matrix to form novel functional materials that can provide both challenges and opportunities for new innovation in optoelectronic and photonic applications. As a proof‐of concept application, we synthesized in situ the first highly soluble conjugated polymer‐covalently functionalized BP derivative (PDDF‐g‐BP) which was used to fabricate a resistive random access memory (RRAM) device with a configuration of Au/PDDF‐g‐BP/ITO. In contrast to PDDF without memory effect, PDDF‐g‐BP‐based device exhibits a nonvolatile rewritable memory performance, with a turn‐on and turn‐off voltages of +1.95 V and ?2.34 V, and an ON/OFF current ratio of 10⁴. The current through the device in both the ON and OFF states is still kept unchanged even at 200th switching cycle. The PDDF/BP blends show a very unstable memory performance with a very small ON/OFF current ratio.     

Formation of a polycrystalline film of donor material on PEDOT:PSS buffer induced by crystal nucleation

Poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is the most popular anode buffer coated on indium tin oxide. It is thought to improve the inorganic–organic contact, but little is known about its role in organic–organic contact. This study addresses the latter issue by examining how the PEDOT:PSS layer affects the crystallization process of the neighboring layer composed of p‐type organic semiconductors in an organic photovoltaic device. Low landing voltage scanning electron microscopic analysis of crystals and aggregates of two donor compounds, tetrabenzoporphyrin (BP) and poly(3‐hexylthiophene) (P3HT), showed that PEDOT:PSS effectively nucleates the crystallization or aggregation of the donor material on its surface to form a uniformly thick film of polycrystalline BP or aggregated P3HT molecules. By contrast, a graphitic surface cannot induce structural order of the donor molecules on it. This result implies that pinning of the donor molecules to the acidic PEDOT:PSS surface promotes the heterogeneous nucleation at the organic–organic interface. © 2014 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 833–841     

Photoexcited States of UV Absorbers,Benzophenone Derivatives

The UV absorption, phosphorescence and phosphorescence‐excitation spectra of benzophenone (BP) derivatives used as organic UV absorbers have been observed in rigid solutions at 77 K. The triplet–triplet absorption spectra have been observed in acetonitrile at room temperature. The BP derivatives studied are 2,2′,4,4′‐tetrahydroxybenzophenone (BP‐2), 2‐hydroxy‐4‐methoxybenzophenone (BP‐3), 2,2′‐dihydroxy‐4,4′‐dimethoxybenzophenone (BP‐6), 5‐chloro‐2‐hydroxybenzophenone (BP‐7) and 2‐hydroxy‐4‐n‐octyloxybenzophenone (BP‐12). The energy levels and lifetimes of the lowest excited triplet (T₁) states of these BP derivatives were determined from the first peak of phosphorescence. The time‐resolved near‐IR emission spectrum of singlet oxygen generated by photosensitization with BP‐7 was observed in acetonitrile at room temperature. BP‐2, BP‐3, BP‐6 and BP‐12 show photoinduced phosphorescence enhancement in ethanol at 77 K. The possible mechanism of the observed phosphorescence enhancement is discussed. The T₁ states of 2‐hydroxy‐5‐methylbenzophenone, 4‐methoxybenzophenone and 2,4′‐dimethoxybenzophenone have been studied for comparison.     

Small Pd nanoparticles supported in large pores of mesocellular foam: an excellent catalyst for racemization of amines

Highly dispersed palladium nanoparticles (1–2 nm) supported in large‐pore mesocellular foam (MCF; 29 nm) were synthesized. The Pd‐nanocatalyst/MCF system was characterized by transmission electron microscopy (TEM), powder X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The performance of the Pd nanocatalyst obtained was examined for amine racemization. The Pd nanocatalyst showed higher activity and selectivity toward racemization of (S)‐1‐phenylethyl amine than any other amine racemization catalyst reported so far and it could be reused several times. Our data from TEM and XRD suggest a restructuring of the Pd nanocatalyst from amorphous to crystalline and an increase in Pd nanocatalyst size during the racemization reaction. This led to an unexpected increase of activity after the first use. The Pd nanocatalyst obtained can be integrated with other resolving processes of racemic organic compounds to increase the yield of chiral organic products.     

Self‐Assembly of Azobenzene Derivatives into Organogels and Photoresponsive Liquid Crystals

A new class of coil–rod–coil molecules with an azobenzene core was synthesized. They were found to form robust organogels in several organic solvents. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), FTIR spectroscopy, UV/Vis absorption spectroscopy, ¹H NMR spectroscopy, and X‐ray diffraction (XRD) revealed that in these organogels, the molecules self‐assembled into a nanofiber network with an H‐type aggregation mode under the joint effect of π–π stacking, intermolecular hydrogen bonding, and van der Waals forces. Interestingly, the incorporation of the azobenzene mesogene into the rigid core led to photoisomerizable liquid crystal materials, which exhibited quick responsiveness to light and temperature, along with the trans–cis transition stimulated by UV light and heating.     

Solution route to inorganic nanobelt‐conducting organic polymer core‐shell nanocomposites

A facile and versatile solution‐based approach was developed to prepare semiconductor metal oxide nanobelt‐conducting organic polymer core‐shell nanocomposites. Well‐defined nanobelts of several types of oxide nanobelts were combined with conducting polymer [polypyrrole (PPy) and polyaniline (PANi)] via in situ polymerization in aqueous solution to obtain a new type of inorganic–organic composite nanostructure. Samples were characterized by using X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, electron energy loss spectra, high‐resolution transmission electron microscopy, and ultraviolet–visible techniques. Electron energy loss spectra revealed the existence of C?C and C? N bonds in coating layers to prove the encapsulation of PPy or PANi. The red‐shift of absorption band at high‐energy was observed for PPy‐encapsulated composites via ultraviolet–visible spectroscopy, and significant absorption band shifts were also encountered to PANi‐encapsulated composites, which suggest possibilities of band‐gap tuning of such metal oxide‐conducting polymer composites to be applied especially in solar cell devices. However, the sacrifice of nanobelts‐core led to hollow structures of PPy and PANi, which expands the synthetic strategies to prepare conducting polymer nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2892–2900, 2005     

Insights into Structure Direction of Microporous Aluminophosphates: Competition between Organic Molecules and Water

A combination of experimental characterisation techniques and computational modelling has allowed us to gain insight into the molecular features governing structure direction in the synthesis of microporous aluminophosphates. The occlusion of three different structure‐directing agents (SDAs), triethylamine (TEA), benzylpyrrolidine (BP) and (S )‐(?)‐N‐benzylpyrrolidine‐2‐methanol (BPM), within the AFI structure during its crystallisation, together with the simultaneous incorporation of water, has been experimentally measured. We found a higher incorporation of organic molecules in the structure obtained with BPM, while a higher water (and lower organic) content is found for the ones obtained with TEA and BP as SDAs. The computational study provides a thermodynamic explanation for the observed behaviour in terms of the relative stabilisation energy of the SDAs and water molecules within the AFI framework compared with when they are in aqueous solution, and demonstrates that a competition for preferential occupation exists between water and organic SDAs, which is a function of the interaction with the inorganic framework. The lower interaction of TEA and BP molecules with the AFI structure promotes the simultaneous incorporation of water molecules in the 12‐membered‐ring (MR) channel, to increase the host–guest interaction energy and thus the thermodynamic stability. The presence of strongly interacting methanol groups in the BPM molecules leads to the incorporation of only organic molecules within the 12‐MR channels. Our results demonstrate the essential role that water molecules play in the stabilisation of hydrophilic microporous aluminophosphates; a minimum amount of organic SDA is, however, essential for a templating role of the microporous architecture.     

Azo‐Polymer Janus Particles Assembled by Solvent‐Induced Microphase Separation and Their Photoresponsive Behavior

We report the successful fabrication of photoresponsive Janus particles (JPs) composed of an epoxy‐based azo polymer and poly(methyl methacrylate) (PMMA). Two representative azo polymers, of which one polymer (BP‐AZ‐CN) has cyano groups as electron‐withdrawing substituents on the azobenzene moieties and the other polymer (BP‐AZ‐CA) has carboxyl groups as the electron‐withdrawing substituents, were adopted for the investigation. The nanoscaled JPs, with a narrow size distribution and different azo polymer/PMMA ratios, were fabricated through self‐assembly in solution and as dispersions. Upon irradiation with linearly polarized light (λ=488 nm), two types of photoresponsive behavior were observed for JPs in the solid state. For JPs composed of BP‐AZ‐CN and PMMA, the light irradiation caused the azo‐polymer component to be stretched along the light polarization direction. Conversely, for JPs composed of BP‐AZ‐CA and PMMA, the azo‐polymer component became separated from PMMA component under the same irradiation conditions. These observations are valuable for a deeper understanding of the nature of self‐assembly and photoinduced mass‐transport at the nanometer scale.     

Remote Sensitized Photoisomerization via Through‐Bond Triplet–Triplet Energy Transfer Mediated by a Salt Bridge in a Supramolecular Dyad

A supramolecular dyad, BP‐(amidinium‐carboxylate)‐NBD is constructed, in which benzophenone (BP) and norbornadiene (NBD) are connected via an amidinium‐carboxylate salt bridge. The photophysical and photochemical properties of the assembled BP‐(amidinium‐carboxylate)‐NBD dyad are examined. The phosphorescence of the BP chromophore is efficiently quenched by the NBD group in BP‐(amidinium‐carboxylate)‐NBD via the salt bridge. Time‐resolved spectroscopy measurements indicate that the lifetime of the BP triplet state in BP‐(amidinium‐carboxylate)‐NBD is shortened due to the quenching by the NBD group. Selective excitation of the BP chromophore results in isomerization of the NBD group to quadricyclane (QC). All of these observations suggest that the triplet–triplet energy transfer occurs efficiently in the BP‐(amidinium‐carboxylate)‐NBD salt bridge system. The triplet–triplet energy transfer process proceeds with efficiencies of approximately 0.87, 0.98 and the rate constants 1.8×10³ s^?1, and 1.3×10⁷ s^?1 at 77 K and room temperature, respectively. The mechanism for the triplet–triplet energy transfer is proposed to proceed via a “through‐bond” electron exchange process, and the non‐covalent bonds amidinium‐carboxylate salt bridge can mediate the triplet–triplet energy transfer process effectively for photochemical conversion.     

First‐Principles Investigation of Anisotropic Electron and Hole Mobility in Heterocyclic Oligomer Crystals

Based on quantum chemistry calculations combined with the Marcus–Hush electron transfer theory, we investigated the charge‐transport properties of oligothiophenes (nTs) and oligopyrroles (nPs) (n=6, 7, 8) as potential p‐ or n‐type organic semiconductor materials. The results of our calculations indicate that 1) the nPs show intrinsic hole mobilities as high as or even higher than those of nTs, and 2) the vertical ionization potentials (VIPs) of the nPs are about 0.6–0.7 eV smaller than the corresponding VIPs of the nTs. Based on their charge‐transport ability and hole‐injection efficiency, the nPs have potential as p‐type organic semiconducting materials. Furthermore, it was also found that the maximum values of the electron‐transfer mobility for the nTs are larger by one‐to‐two orders of magnitude than the corresponding maximum values of hole‐transfer mobility, which suggests that the nTs have the potential to be developed as promising n‐type organic semiconducting materials owing to their electron mobility.     

One‐component photoinitiator based on benzophenone and sesamol

A new benzodioxole derivative, 4‐(1,3‐benzodioxol‐5‐yloxy) benzophenone (BPBDO), based on benzophenone and sesamol was precisely synthesized, and it can be used as a 1‐component type II photoinitiator. Elementary analysis, atmospheric pressure chemical ionization mass spectrometry, ¹H nuclear magnetic resonance, and ¹³C nuclear magnetic resonance studies revealed that the molecular structure of BPBDO consisted of both benzophenone (BP) and benzodioxole (BDO) structures. The laser flash photolysis experiments and electron spin resonance test indicated that the process of radicals generated from BPBDO after irradiation was similar to 3 processes of ethyl 4‐dimethylaminobenzoate and BP. The kinetics of photopolymerization of the photoinitiator was also studied by real‐time infrared spectroscopy. The oxygen content, light intensity, and viscosity of the monomer affected the decomposition (R_d) and polymerization rate, and the final double bond conversion was also studied. All the results suggest that BPBDO is a 1‐component photoinitiator that is an efficient photoinitiator for free radical polymerization. In contrast to typical dual‐component photoinitiators, eg, BP/ethyl 4‐dimethylaminobenzoate or BP/BDO, BPBDO does not require an additional amine coinitiator for the initiation and is applicable in nonamine resin systems.     

Synthesis and characterization of a biphenyl perfluorocyclobutyl (BP‐PFCB) polyethylene glycol (PEG) blend compatibilizer

Polyethylene glycol (PEG) end‐capped trifluorovinyl ether (TFVE) telechelomer was synthesized in one step via esterification of 4‐(trifluorovinyloxy) benzoic acid. The new telechelomer was characterized by attenuated total reflectance Fourier transform infrared (ATR‐FTIR), elemental analysis, and by ¹⁹F and ¹H nuclear magnetic resonance (NMR) spectroscopy. The telechelomer and 4,4′‐bis(4‐trifluorovinyloxy)biphenyl (BPVE) were thermally copolymerized via step‐growth [2 + 2] cycloaddition at 160°C. The polymerization afforded PEG enchained biphenyl perfluorocyclobutyl (BP‐PFCB) copolymers that are solution processable and film forming. These copolymers were characterized by ATR‐FTIR, ¹⁹F NMR, and ¹H NMR. Gel permeation chromatography (GPC) gave number‐average molecular weight (M_n) ranging 11,000 to 12,000. Compatibilization of PEG and a commercial polymer BP‐PFCB was achieved utilizing the new PEG BP‐PFCB copolymer, 3‐co2‐4 . It was found that 5 wt% of 3 ‐ co2 ‐ 4 was ideal to reduce interfacial tension by scanning electron microscope (SEM). In addition, phase homogeneity was studied by differential scanning calorimetry (DSC). Copyright © 2016 John Wiley & Sons, Ltd.     

Bi‐anchoring Organic Dyes that Contain Benzimidazole Branches for Dye‐Sensitized Solar Cells: Effects of π Spacer and Peripheral Donor Groups

Benzimidazole‐branched bi‐anchoring organic dyes that contained triphenylamine/phenothiazine donors, 2‐cyanoacrylic acid acceptors, and various π linkers were synthesized and examined as sensitizers for dye‐sensitized solar cells. The structure–activity relationships in these dyes were systematically investigated by using absorption spectroscopy, cyclic voltammetry, and density functional theory calculations. The wavelength of the absorption peak was more‐heavily influenced by the nature of the π linker than by the nature of the donor. For a given donor, the absorption maximum (λ_max) was red‐shifted on changing the π linker from phenyl to 2,2′‐bithiophene, whilst the dyes that contained triphenylamine units displayed higher molar extinction coefficients (?) than their analogous phenothiazine‐based triphenylamine dyes, which led to good light‐harvesting properties in the triphenylamine‐based dyes. Electrochemical data for the dyes indicated that the triphenylamine‐based dyes possessed relatively low‐lying HOMOs, which could be beneficial for suppressing back electron transfer from the conduction band of TiO₂ to the oxidized dyes, owing to facile regeneration of the oxidized dye by the electrolyte. The best performance in the DSSCs was observed for a dye that possessed a triphenylamine donor and 2,2′‐bithiophene π linkers. Electron impedance spectroscopy (EIS) studies revealed that the use of triphenylamine as the donor and phenyl or 2,2′‐bithiophene as the π linkers was beneficial for disrupting the dark current and charge‐recombination kinetics, which led to a long electron lifetime of the injected electrons in the conduction band of TiO₂.     

Naphthalene‐Diimide‐Based Ionenes as Universal Interlayers for Efficient Organic Solar Cells

Self‐doping ionene polymers were efficiently synthesized by reacting functional naphthalene diimide (NDI) with 1,3‐dibromopropane ( NDI‐NI ) or trans‐1,4‐dibromo‐2‐butene ( NDI‐CI ) via quaternization polymerization. These NDI‐based ionene polymers are universal interlayers with random molecular orientation, boosting the efficiencies of fullerene‐based, non‐fullerene‐based, and ternary organic solar cells (OSCs) over a wide range of interlayer thicknesses, with a maximum efficiency of 16.9 %. NDI‐NI showed a higher interfacial dipole (Δ), conductivity, and electron mobility than NDI‐CI , affording solar cells with higher efficiencies. These polymers proved to efficiently lower the work function (WF) of air‐stable metals and optimize the contact between metal electrode and organic semiconductor, highlighting their power to overcome energy barriers of electron injection and extraction processes for efficient organic electronics.     

A Potential Carcinogenic Pyrene Derivative under Förster Resonance Energy Transfer to Various Energy Acceptors in Nanoscopic Environments

Picosecond‐resolved Förster resonance energy transfer (FRET) from various vibronic bands in benzo[a]pyrene (BP) shows a strong dependency on the spectral overlap of an energy acceptor in a confined environment. Our study on the dipolar interactions between BP and different acceptors, including ethidium (Et), acridine orange (AO), and crystal violet (CV), at the surface of a model anionic micelle revealed that the Förster distance (R₀) and the rate of energy transfer is dependent on the individual spectral overlap of the vibronic bands of BP with the absorption spectra of the different energy acceptors. The differential behavior of the vibronic bands is compared with that of different dyes [quantum dots (QDs)] in a “dye‐blend” (mixture) under FRET to an energy acceptor. Comparison of the FRET of the QDs with that of BP confirmed the independent nature of the dipolar interaction of the vibronic bands with other organic molecules, and the use of deconvolution techniques in the interpretation of the donor–acceptor (D –A) distance was also justified. We also showed that the consideration of differential FRET from the vibronic bands of BP and from the QDs in the dye‐blend is equally acceptable in theoretical frameworks including the Infelta–Tachiya model and D –A distribution analysis in nanoenvironments.     

Self‐Sorting of Four Organic Molecules into a Heterowheel Polypseudorotaxane

The social self‐sorting supramolecular assembly is described by non‐covalent interactions among four organic components. Toward this goal, a series of self‐sorting systems have been investigated by mixing two or three different compounds; naphthyl‐bridged bis(α‐cyclodextrin), N,N′‐dioctyl‐4,4′‐bipyridinium, 2,6‐dihydroxynaphthalene, and cucurbit[8]uril. The influence of alkyl chains of viologen derivatives and the binding abilities of these systems have also been studied. Their integrative self‐sorting led to the exclusive formation of the purple supramolecular heterowheel polypseudorotaxane. The heterowheel polypseudorotaxane is a thermodynamically stable self‐sorted product, and consists of two different macrocycles with three sorts of different non‐covalent interactions. Its structure was established by NMR spectroscopy and UV/Vis absorption spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light‐scattering (DLS), diffusion‐ordered spectroscopy (DOSY), and viscosity measurements.     

Photoelectrochemical studies on aqueous suspensions of 3‐dodecyl 2–5 di‐thionyl pyrrole/metal oxide photoactive interfaces

Colloidal ZnO, Fe₂O₃ and Cu₂O solutions were used to explore photonic activities at metal oxides/organic semiconductors interfaces. Fluorescence spectroscopic and dynamic electrochemical techniques were performed on colloidal metal oxides articles modified with 3‐dodecyl 2–5 di‐thionyl pyrrole (3‐DODTh‐Py) to investigate the quantum absorbance efficiency at this inorganic/organic interface (IOI). The IOI assemblies were p‐n junction‐type interfaces, where 3‐DODTh‐Py) functions as electron donor. Results were interpreted using the optical and electrochemical parameters of the organic monomer such as IP (ionization potential), EA (electron affinity), and E_g (Energy band gap), and the barrier height at the IOI interface. One of the driving forces for great absorption at IOI was the great difference in electronegativity between inorganic and organic interface. Copyright © 2011 John Wiley & Sons, Ltd.     

A Main‐Group Element Radical Based One‐Dimensional Magnetic Chain

The first main‐group element radical based one‐dimensional magnetic chain ( 1K )_n was realized by one‐electron reduction of the pyridinyl functionalized borane 1 with elemental potassium in THF in the absence of 18‐crown‐6 (18‐c‐6). The electron spin density of ( 1K )_n mainly resides at the boron centers with a considerable contribution from central benzene and pyridine moieties. The spin centers exhibit an antiferromagnetic interaction as demonstrated by magnetic measurements and theoretical calculations. In contrast, the reduction in the presence of 18‐c‐6 afforded the separated radical anion salt 1K(Crown) , in which the potassium cation was trapped by THF and 18‐c‐6 molecules. Further one‐electron reduction of 1K(Crown) and ( 1K )_n led to the diamagnetic monomer and polymer, respectively.     

Light‐emitting diodes and lasers based on polymer films doped with small organic molecules and rare‐earth complexes

We investigated the lasing properties of optically pumped polymer films. Amplified spontaneous emission (ASE) around 400 nm was observed in polymer films of polystyrene (PS) and poly(N‐vinylcarbazole) (PVK) doped up to 20% with the hole‐transporting organic molecule N,N′‐bis(3‐methylphenyl)‐N,N′‐diphenylbenzidine (TPD). Thus, TPD‐based films are candidates for blue‐emitting organic diode lasers. Films containing several semiconducting organic molecules and polymers and rare‐earth complexes were also investigated. Energy transfer was observed in PVK films doped with various europium and samarium complexes. PS films containing the electron‐transporting organic molecule 2‐(4‐biphenylyl)‐5‐(4‐tert‐butylphenyl)‐1,3,4‐oxadiazole and small amounts of TPD also showed energy transfer to the europium complexes, but not to the samarium ones. None of these films demonstrated ASE; therefore, they are not appropriate for lasing purposes. However, because rare‐earth ions have very sharp emission spectra, these materials are candidates for very monochromatic light‐emitting diodes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2706–2714, 2003