Post-Formation of Fused Pentagonal Structure on Fjord Region of Polyaromatic Hydrocarbons under Hydrothermal Conditions.

This study explores the synthesis of cyclopenta-fused polyaromatic hydrocarbons (CP-PAHs) via Pt-catalyzed cyclization in water, focusing on the formation of fused pentagonal rings within heavily fused PAH frameworks. Utilizing platinum catalysts at lower temperatures (200-260 °C) in water, led to the successful synthesis of singly cyclized CP-PAHs. The reaction conditions facilitated the mono-cyclization of substrates such as dibenzo[g,p]chrysene and its isomers, yielding the desired products while suppressing the formation of bis-cyclized compounds. The use of Fe2O3 as an additive in conjunction with PtO2 was effective to suppress hydrogenation of the substrates and products. The products exhibited a redshift in UV-visible absorption and photoluminescence bands due to a decrease in the HOMO-LUMO energy gap. These findings highlight the potential of Pt-catalyzed cyclization for the controlled synthesis of CP-PAHs, with implications for various applications in materials science.

Circularly polarized luminescence and high photoluminescence quantum yields from rigid 5,10-dihydroindeno[2,1-a]indene and 2,2'-dialkoxy-1,1'-binaphthyl conjugates and copolymers.

5,5,10,10-Tetramethyl-5,10-dihydroindeno[2,1-a]indene (COPV1(Me)) was installed into either the 3,3'- or 6,6'-positions of chiral 2,2'-dioctyloxy-1,1'-binaphthyl to afford 2 : 1 conjugates (monomeric compounds) and 1 : 1 copolymers. These compounds showed high photoluminescence quantum yields of >0.95 whilst also exhibiting circular dichroism (CD) and circularly polarized luminescence (CPL). The dissymmetry factors of CPL (gCPL) for the 3,3'- and 6,6'-monomeric compounds in THF were 6.6 × 10-4 and 3.3 × 10-4, respectively. The 3,3'-isomer has a higher g value than the 6,6'-isomer, which was attributed to the difference in the extent of π-conjugation and the angle between electronic and magnetic transition moments. The gCPL values of the 3,3'-linked and 6,6'-linked copolymers were 1.1 × 10-3 and 6.8 × 10-4, respectively. The structural rigidity of the COPV units is beneficial to achieve relatively high g values whilst maintaining a photoluminescence quantum yield that is close to unity by using a single type of fluorophore.

Water Fraction Dependence of the Aggregation Behavior of Hydrophobic Fluorescent Solutes in Water-Tetrahydrofuran.

This work investigates the water fraction dependence of the aggregation behavior of hydrophobic solutes in water-tetrahydrofuran (THF) and the elucidation of the role of THF using fluorescence microscopy, dynamic light scattering, neutron and X-ray scattering, and photoluminescence measurements. On the basis of the obtained results, the following model is proposed: hydrophobic molecules are molecularly dispersed in the low-water-content region (10-20 vol %), while they form mesoscopic particles upon increasing the water fraction to ∼30 vol %. This abrupt change is due to the composition fluctuation of the water-THF binary system to form hydrophobic areas in THF, followed by THF-rich droplets where hydrophobic solutes are incorporated and form loose aggregates. Further increasing the water content prompts the desolvation of THF, which decreases the particle size and generates tight aggregates of solute molecules. This model is consistent with the luminescence behavior of the solutes and will be helpful to control the aggregation state of hydrophobic solutes in various applications.

Preparation of 2,3-Dibromo-1H-indenes and Tetrabromodihydro-s-indacenes as Synthetic Building Blocks.

The acid-induced intramolecular cyclization of 1,1-disubstituted 3-aryl-2,3-dibromoallylalcohols affords 2,3-dibromo-1H-indene derivatives. This method is also applicable to the preparation of tetrabromodihydro-s-indacenes. The thus obtained multi-brominated compounds can serve as versatile synthetic building blocks to obtain a variety of indene and indacene derivatives, as demonstrated by the synthesis of dialkylmethylene-bridged oligo(phenylenevinylene)s, which feature attractive photophysical properties.

Long-wavelength visible to near infrared photoluminescence from carbon-bridged styrylstilbene and thiadiazole conjugates in organic and aqueous media.

Donor-acceptor-donor conjugates composed of electron-donating carbon-bridged styrylstilbene (COPV2) and electron-accepting thiadiazole derivatives equipped with carbazolyl (Cz) terminators, Cz-COPV2-A-COPV2-Cz (A = benzothiadiazole (BTz), naphthobis(thiadiazole) (NTz), or benzobis(thiadiazole) (BBTz)), were newly synthesized and found to serve as efficient and stable long-wavelength photoluminescent dyes in organic and aqueous media. In particular, Cz-COPV2-BBTz-COPV2-Cz showed photoluminescence in the near infrared region (895-927 nm) with a photoluminescence quantum yield (PLQY) of up to 0.19 in cyclohexane and of 0.02-0.03 in THF/water mixtures. Its analogues with weaker acceptors, Cz-COPV2-BTz-COPV2-Cz and Cz-COPV2-NTz-COPV2-Cz, showed yellow to deep-red emission in organic solvents, with PLQYs of up to 0.71 in organic solvents and 0.45 in THF/water mixtures.

Single-Crystalline Optical Microcavities from Luminescent Dendrimers.

Microcrystallites are promising minute mirrorless laser sources. A variety of luminescent organic compounds have been exploited along this line, but dendrimers have been inapplicable owing to their fragility and extremely poor crystallinity. Now, a dendrimer family that overcomes these difficulties is presented. First-, second-, and third-generation carbazole (Cz) dendrimers with a carbon-bridged oligo(phenylenevinylene) (COPV2) core (GnCOPV2, n=1-3) assemble to form microcrystals. The COPV2 cores align uni/bidirectionally in the crystals while the Cz units in G2- and G3COPV2 align omnidirectionally. The dendrons work as light-harvesting antennas that absorb non-polarized light and transfer it to the COPV2 core, from which a polarized luminescence radiates. Furthermore, these crystals act as laser resonators, where the lasing thresholds are strongly coupled with the crystal morphology and the orientation of COPV2, which is in contrast with the conventional amorphous dendrimers.

Carbon-Bridged Oligo(phenylene vinylene)s: A de Novo Designed, Flat, Rigid, and Stable π-Conjugated System.

The modern history of conducting organic systems started with a fortuitous error in 1967 on acetylene polymerization, followed by a rational discovery in 1976 on the effects of doping that generates a polaron and, hence, dramatically increases conductivity. Not unexpectedly, however, the prototypical polyacetylene suffers many problems, including C-C single bond rotation, short effective conjugation length, radiationless deactivation, and instability of the polarons. Several strategies have been put in place to solve these problems. An early approach relied on partial rigidification of the polyene structure by conversion into polymers with thiophene, pyrrole, and benzene linkages. An oligo(phenylene vinylene) (OPV) is an all-carbon analogue of polyacetylene, where every other diene unit in the polyene chain is converted to a benzene unit, still leaving many C-C single bonds freely rotating in the molecule. We considered adding additional carbon bridges to rigidify the OPV skeleton entirely to create a carbon-bridged OPV (COPV). Making such a compound was an obvious challenge. This Account describes the authors' efforts to design and synthesize a series of COPV molecules, where the benzene rings in OPV are bridged by sp3 carbon atoms to form a bicyclo[3.3.0]octatriene framework bearing a tetrasubstituted olefin at the ring fusion. This olefinic bond is so strained that it resists further deformation or conversion to sp3 centers, and hence, it is chemically stable despite the strain. The sp3 carbon bridges can bear organic side chains that hinder intermolecular interactions, rendering the excited states stable and long-lived even in the solid state. They also increase solubility, a common problem among rigid molecular systems. With these structural features, the COPV molecules were found to be well behaved both at a single-molecule level and as a bulk material. We reported in 2009 a method for the synthesis of COPVs and have, since then, reported their structures and physicochemical properties, including basic photophysical properties of neutral and charged derivatives, thermal and photostability, and fast electron transfer. These properties have rendered the COPV molecules useful for electronic and photonic research, for example, lasers, solar cells, and molecular wire applications. Noteworthy discoveries in the area connecting chemistry and physics include inelastic tunneling and long-range resonance tunneling at ambient temperature, which were previously observed only for organic molecular wires placed under cryogenic conditions. Given the ready availability of the COPV skeleton bearing a wide variety of substituents, this class of molecules will serve as versatile building blocks for fundamental and applied research on physicochemical and materials chemistry.

Carbon-bridged Oligo(phenylenevinylene)s as Light-harvesting Antenna for Porphyrins.

The efficacy of carbon-bridged oligo(phenylenevinylenes)s (COPVs) as light-harvesting antenna for porphyrins is demonstrated using a series of 5,15-di-COPVn-substituted free-base and zinc porphyrins, COPVn-MP-COPVn (n=1-3, M=H2 , Zn). These molecules were synthesized by Suzuki-Miyaura cross-coupling reactions of COPVn-Bpin and Br-H2 P-Br. The absorption spectra of these compounds in solution show a significant expansion of the Soret band region together with a bathochromic shift of the Q band, suggesting a significant interaction between these chromophores in the ground state. The photoluminescence quantum yield of the porphyrin-COPV conjugates is enhanced up to four times relative to the parent porphyrins. Theoretical calculations also indicated interactions between these chromophores in the HOMO, which suggests that the light-harvesting ability stems from the expansion of the π-electron-conjugation system.

π-Electronic Co-crystal Microcavities with Selective Vibronic-Mode Light Amplification: Toward Förster Resonance Energy Transfer Lasing.

π-conjugated organic microcrystals often act as optical resonators in which the generated photons in the crystal are confined by the reflection at the crystalline facets and interfere to gain lasing action. Here, we fabricate microcrystals from a mixture of carbon-bridged oligo- para-phenylenevinylenes (COPVs) with energy-donor (D) and energy-acceptor (A) characters. Upon weak excitation of the single D-A co-crystal, Förster resonance energy transfer (FRET) takes place, exhibiting spontaneous emission from A. In contrast, upon strong pumping, stimulated emission occurs before FRET, generating lasing action from D. Lasing occurs with single- and dual-vibronic levels, and the lasing wavelength can be modulated by the doping amount of A. Time-resolved spectroscopic studies reveal that the rate constant of lasing is more than 20 times greater than that of FRET. Furthermore, microcrystals, vertically grown on a Ag-coated substrate, reduce the lasing threshold by one-fourth. This study proposes possible directions toward organic solid FRET lasers with microcrystalline resonators.

Coherent Resonant Electron Tunneling at 9 and 300 K through a 4.5 nm Long, Rigid, Planar Organic Molecular Wire.

Organic molecular wires that operate stably at ambient temperatures are a necessary first step toward practical and useful molecular-scale electronic devices, which have thus far been hampered by many factors, including the structural and electron configurational instability of organic molecules. We report here that a single disulfanyl carbon-bridged oligo(phenylenevinylene) (COPV6) molecule embedded between thermally stable electroless Au-plated electrodes of a 4 nm nanogap undergoes coherent resonant tunneling at both 9 and 300 K and functions even after storage in air at room temperature. Such enormous stability is ascribed to the unique structural characteristics of COPV6, that is, rigidity, planarity, thermal stability, resistivity against oxidation and reduction, and an organic insulating sheath that protects the π-system. When sandwiched between the gaps without pinning, this molecule behaves as a Coulomb island with sequential single-electron tunneling at 9 K that disappears at 300 K while maintaining a stable electron flow.

Bis(aminoaryl) Carbon-Bridged Oligo(phenylenevinylene)s Expand the Limits of Electronic Couplings.

Carbon-bridged bis(aminoaryl) oligo(para-phenylenevinylene)s have been prepared and their optical, electrochemical, and structural properties analyzed. Their radical cations are class III and class II mixed-valence systems, depending on the molecular size, and they show electronic couplings which are among the largest for the self-exchange reaction of purely organic molecules. In their dication states, the antiferromagnetic coupling is progressively tuned with size from quinoidal closed-shell to open-shell biradicals. The data prove that the electronic coupling in the radical cations and the singlet-triplet gap in the dications show similar small attenuation factors, thus allowing charge/spin transfer over rather large distances.

Design and Functions of Semiconducting Fused Polycyclic Furans for Optoelectronic Applications.

The fused polycyclic furan structure is a ubiquitous motif in naturally occurring organic compounds. However, they had been rarely seen in the literature of organic electronic research until very recently, probably because of the lack of stability of simple furans under conditions that the compounds experience in the active layer of the device. Nonetheless, from the viewpoint of molecular structure, furans look to have potential merits as organic semiconductors such as thiophenes, which are more popular in the organic electronic area. For example, the small atomic radius and large electronegativity of oxygen will increase intermolecular molecular orbital (MO) overlap and hence facilitate charge transporting ability in the solid state. In this Account, we describe the molecular design and optoelectronic applications of fused polycyclic furans, such as benzodifurans (BDFs), naphthodifurans (NDFs), and anthradifurans (ADFs). The molecular design that was exploited in this study crucially depends on the synthetic flexibility of a "modular" synthetic strategy that we purposely developed and reviewed in a separate report. Our synthetic strategy comprises two steps carried out in situ: cyclization of an o-alkynylphenol into a zincio benzofuran and its electrophilic Negishi-type trapping to obtain a range of multisubstituted fused furan compounds. These compounds are found to possess electronic structures resembling those of fused polyaromatic hydrocarbons, such as acenes or phenacenes, rather than oxygen-bridged phenylenevinylene, along with unique characteristics: a wide HOMO-LUMO gap originating from the weak aromaticity of the furan rings, an intense photoluminescent character, and mechanofluorochromism. Semiconducting properties of fused furans are also excellent among organic materials: some BDF derivatives show high hole mobility on the order of 10-3 cm2/(V s) in the amorphous state using time-of-flight (TOF) technique. The p-type BDFs exhibit high performance as hole-transporting material in heterojunction organic light-emitting diodes (OLEDs), while carbazole-substituted BDFs (CZBDFs) are ambipolar with well-balanced high carrier mobility for both hole and electron and serve as host materials for full-color electroluminescence in both hetero- and homojunction architectures. More π-expanded NDFs showed good crystallinity and are effective active materials for organic field-effect transistors (OFETs) with a high hole mobility of up to 3.6 cm2/(V s) using a solution process. These studies have illustrated the high potential of fused polycyclic furans in organic electronics research, which thus far have attracted much less attention than their thiophene congeners.

Three-Dimensionally Homoconjugated Carbon-Bridged Oligophenylenevinylene for Perovskite Solar Cells.

Stabilization of the radical cationic state of a donor molecule by 3-D homoconjugation was probed using a substituted carbon-bridged oligophenylenevinylene backbone (COPV, or 5,5-diarylindeno[2,1-a]indenes). For molecules bearing electron-donating groups as the 5,5-aryl moieties, a one-electron oxidation of the COPV backbone results in delocalization of the cationic charge over the whole molecule with a small reorganization energy. The compounds forming a stable radical cation by 3-D homoconjugation produce a uniform amorphous film and show high short-circuit current, high fill factor, and hence high power-conversion efficiency when used as a hole-transporting layer of an organic-inorganic hybrid lead perovskite solar cell. This material thus shows a performance and stability in air comparable to those obtained with the benchmark material, spiro-MeOTAD.

Electronic Transitions in Conformationally Controlled Peralkylated Hexasilanes.

The photophysical properties of oligosilanes show unique conformational dependence due to σ-electron delocalization. The excited states of the SAS, AAS, and AEA conformations of peralkylated n-hexasilanes, in which the SiSiSiSi dihedral angles are controlled into a syn (S), anti (A), or eclipsed (E) conformation, were investigated by using UV absorption, magnetic circular dichroism (MCD), and linear dichroism spectroscopy. Simultaneous Gaussian fitting of all three spectra identified a minimal set of transitions and the wavenumbers, oscillator strengths, and MCD B terms in all three compounds. The results compare well with those obtained by using the symmetry-adapted-cluster configuration interaction method and almost as well with those obtained by time-dependent density functional theory with the PBE0 functional. The conformational dependence of the transition energies and other properties of free-chain permethylated n-hexasilane, n-Si6 Me14 , was also examined as a function of dihedral angles, and the striking effects found were attributed to avoided crossings between configurations of σσ* and σπ* character.

Carbon-bridged oligo(p-phenylenevinylene)s for photostable and broadly tunable, solution-processable thin film organic lasers.

Thin film organic lasers represent a new generation of inexpensive, mechanically flexible devices for spectroscopy, optical communications and sensing. For this purpose, it is desired to develop highly efficient, stable, wavelength-tunable and solution-processable organic laser materials. Here we report that carbon-bridged oligo(p-phenylenevinylene)s serve as optimal materials combining all these properties simultaneously at the level required for applications by demonstrating amplified spontaneous emission and distributed feedback laser devices. A series of six compounds, with the repeating unit from 1 to 6, doped into polystyrene films undergo amplified spontaneous emission from 385 to 585 nm with remarkably low threshold and high net gain coefficients, as well as high photostability. The fabricated lasers show narrow linewidth (<0.13 nm) single mode emission at very low thresholds (0.7 kW cm(-2)), long operational lifetimes (>10(5) pump pulses for oligomers with three to six repeating units) and wavelength tunability across the visible spectrum (408-591 nm).

Planarization, fusion, and strain of carbon-bridged phenylenevinylene oligomers enhance π-electron and charge conjugation: a dissectional vibrational Raman study.

We have used Raman spectroscopy to study the molecular and electronic structures of the radical cations and dications of carbon-bridged oligo(para-phenylenevinylene)s (COPVn, n = 1-6) possessing consecutive fused pentagons and hexagons, up to 19, along with COPV derivatives having electron-donating and -withdrawing groups. This study was made possible by the outstanding stability of the charged states of COPVs. We could untangle the effects of π-conjugation in the planar structure on the Raman frequency by distinguishing it from other structural effects, such as strain in the vinylene groups shared by the two pentagons. The analyses showed that the radical cations have benzo-quinoidal structures confined in the center of the molecule, as well as benzo-aromatic rings at the terminal sites. In contrast, dications of COPVn longer than n = 3 exhibit a biradicaloid character because of the recovery of aromaticity in the central rings and quinoidal rings at the terminal positions. These biradicaloids favor a singlet nature in their ground electronic states because of the double spin polarization. The introduction of electron-donating and -withdrawing groups on the termini of a COPV core affords, upon oxidation or reduction, a fully delocalized class III mixed valence system because of the high degree of conjugation of the COPV platform, which favors extensive charge delocalization.

The hydrogen/deuterium isotope effect of the host material on the lifetime of organic light-emitting diodes.

The hydrogen/deuterium primary kinetic isotope effect provides useful information about the degradation mechanism of OLED host materials. Thus, replacement of labile C-H bonds in the host with C-D bonds increases the device lifetime by a factor of five without loss of efficiency, and replacement with C-C bonds by a factor of 22.5.

Electron transfer through rigid organic molecular wires enhanced by electronic and electron-vibration coupling.

Electron transfer (ET) is a fundamental process in a wide range of biological systems, photovoltaics and molecular electronics. Therefore to understand the relationship between molecular structure and ET properties is of prime importance. For this purpose, photoinduced ET has been studied extensively using donor-bridge-acceptor molecules, in which π-conjugated molecular wires are employed as bridges. Here, we demonstrate that carbon-bridged oligo-p-phenylenevinylene (COPV), which is both rigid and flat, shows an 840-fold increase in the ET rate compared with the equivalent flexible molecular bridges. A 120-fold rate enhancement is explained in terms of enhanced electronic coupling between the electron donor and the electron acceptor because of effective conjugation through the COPVs. The remainder of the rate enhancement is explained by inelastic electron tunnelling through COPV caused by electron-vibration coupling, unprecedented for organic molecular wires in solution at room temperature. This type of nonlinear effect demonstrates the versatility and potential practical utility of COPVs in molecular device applications.

Electronic transitions in conformationally controlled tetrasilanes with a wide range of SiSiSiSi dihedral angles.

Unlike π-electron chromophores, the peralkylated n-tetrasilane σ-electron chromophore resembles a chameleon in that its electronic spectrum changes dramatically as its silicon backbone is twisted almost effortlessly from the syn to the anti conformation (changing the SiSiSiSi dihedral angle ω from 0 to 180°). A combination of UV absorption, magnetic circular dichroism (MCD), and linear dichroism (LD) spectroscopy on conformationally controlled tetrasilanes 1-9, which cover fairly evenly the full range of angles ω, permitted a construction of an experimental correlation diagram for three to four lowest valence electronic states. The free chain tetrasilane n-Si4 Me10 (10), normally present as a mixture of three enantiomeric conformer pairs of widely different angles ω, has also been included in our study. The spectral trends are interpreted in terms of avoided crossings of 1B with 2B and 2A with 3A states, in agreement with SAC-CI calculations on the excited states of 1-7 and conformers of 10.

Synthesis, crystal packing, and ambipolar carrier transport property of twisted dibenzo[g,p]chrysenes.

A versatile method for the synthesis of dibenzo[g,p]chrysene (DBC) derivatives based on regio- and stereoselective stannyllithiation to diarylacetylenes is described. This method affords a variety of DBCs possessing both electron-donating and electron-withdrawing functional groups. These twisted molecules take brickwork packing structures in single crystals. Thus, ambipolar carrier transport properties with mobility values of up to 10(-3)  cm(2) V(-1) s(-1) in the amorphous state were achieved. Functional groups on DBC frameworks are considered to increase carrier mobility through the enhancement of intermolecular interactions in the brickwork packing structures.