Efficient Bottom‐Up Preparation of Graphene Nanoribbons by Mild Suzuki–Miyaura Polymerization of Simple Triaryl Monomers

Herein an efficient bottom‐up solution‐phase synthesis of N=9 armchair graphene nanoribbons (GNRs) is described. Catalyzed by Pd(PtBu₃)₂, Suzuki–Miyaura polymerization of a simple and readily available triaryl monomer provides a novel GNR precursor with a high molecular weight and excellent solubility. Upon cyclodehydrogenation, the resulting GNR exhibits semiconducting properties with an approximately 1.1 eV band gap (LUMO: ?3.52 eV; HOMO: ?4.66 eV) as characterized by UV/Vis‐NIR spectroscopy and cyclic voltammetry.     

Acid-Modulated Synthesis of Novel π-Conjugated Microporous Polymers for Efficient Metal-Free Photocatalytic Hydrogen Evolution

Simple synthetic modifications that tune the molecular structures, thereby the properties of the molecules, are of topical interest. Herein, we report the synthesis of two novel cationic rosaniline-based conjugated microporous polymers (CMPs) from identical monomers via simple acid modulation (Acetic acid and BF₃ ⋅ Et₂O). The condensation reaction of rosaniline with 2,4,6-triformylphloroglucinol in acetic acid renders β-ketoenamine-linked CMP ( CMP-A ) while changing the acid to BF₃ ⋅ Et₂O, the linkages transform to enol and undergoes BF₂-complexation, leading to boranil CMP ( CMP-B ). BF₂-functionalities in boranil CMP significantly modified the optical and functional properties compared to β-ketoenamine-linked CMP. The cationic-delocalization along with the extended π-delocalization supported by chromophoric BF₂-groups allow CMP-B to exhibit broad absorption spanning the visible to Near-Infrared region (NIR). The absorption red-edge of CMP-B appears around 1277 nm (optical band gap ∼1.58 eV) while CMP-A displays at 981 nm (optical band gap ∼1.83 eV). Most interestingly, as a photocatalyst, CMP-B catalyzes hydrogen evolution with a superior rate of 252 μmol g⁻¹ over CMP-A (100 μmol g⁻¹). It is about 2.5 times higher performance. The transient photocurrent measurements, electrochemical impedance data, and in-depth mott-Schottky analysis demonstrate that the BF₂-group in CMP-B generates photoinduced charge carriers and their migration towards the active sites for photocatalysis. These polymers show significant photocatalytic H₂ generation without any supportive metal co-catalyst. The BF₂ complexed building blocks are a unique class of metal-free photocatalysts for hydrogen evolution through green and cost-effective approach.     

A spectroscopic ellipsometry study of PET membranes from IR to Vis-FUV

A detailed study of Spectroscopic Ellipsometry (SE) spectra of uniaxially stressed, 12μm thick poly(ethylene terephthalate) (PET) membranes were realized in both IR (900-3500 cm⁻¹) and Vis-FUV (1.5 to 6.5 eV) spectral regions and in various orientation angles ∅︁ between the plane of incidence and the machine direction (MD) of the PET membranes. In the IR spectra, the three main modes of the ester group at ∼1126, 1256 and 1721 cm⁻¹ are observed. The first two of these peaks show identical polarization dependence, with preferential orientation ∅︁≈0° (i.e. the plane of reflection parallel to the MD), while the peak at ∼1721 cm⁻¹ is excited in the perpendicular direction, ∅︁≈90°. In the Vis-FUV SE spectra, the dependence of the characteristic electronic absorption bands on the orientation angle ∅︁ is studied. Besides the well known benzene band centered at ∼5 eV, a doublet of less intense peaks appear just above the absorption edge between 4.1 and 4.3 eV with the most striking characteristic that they show polarization selection rules opposing to that of the benzene band. The above characteristics of the electronic Vis-FUV spectra of PET are discussed in a manner comparative to the corresponding IR spectra. The discussion becomes in the context of determining the molecular orientation of PET using a non-destructive technique such as SE.     

t-Si64: A Novel Silicon Allotrope

Utilizing first principle calculations, a novel Si₆₄ silicon allotrope in the I4₁/amd space group with tetragonal symmetry (denoted as t-Si₆₄ below) is proposed in this work. In addition, also its structural, anisotropic mechanical, and electronic properties along with its minimum thermal conductivity κ_min were predicted. The mechanical and thermodynamic stability of t-Si₆₄ were evaluated by means of elastic constants and phonon spectra. The electronic band structure indicates that t-Si₆₄ is an indirect band gap semiconductor with a band gap: 0.67 eV (primitive cell) compared to a direct band gap of 0.70 eV with respect to a conventional cell. The minimum thermal conductivity of t-Si₆₄ (0.74 W cm⁻¹ K⁻¹) is much smaller than that of diamond silicon (1.13 W cm⁻¹ K⁻¹). Therefore, Si−Ge alloys in the I4₁/amd space group are potential thermoelectric materials.     

Annulated Azuleno[2,1,8-ija]azulenes: Synthesis and Properties

Non-alternant non-benzenoid hydrocarbons exhibit very different optical and electronic properties than their well-studied benzenoid analogues. However, preparing such structures with extended conjugation length, remains challenging. Herein, we report the synthesis and properties of azuleno[2,1,8-ija]azulene derivatives using a two-step sequence involving a four-fold aldol condensation between aromatic dialdehydes and readily available tetrahydropentalene-2,5-(1H,3H)-dione. Molecules with band gap values ranging from 1.69 to 2.14 eV and molar extinction coefficients (ϵ) of nearly 3×10⁵ M⁻¹ cm⁻¹ have been prepared. These annulene-like structures exhibit significant diatropic ring currents (aromatic), as supported by ¹H NMR spectroscopy and DFT calculations. Field-effect transistors (OFETs) using azuleno[2,1,8-ija]azulene derivatives as semiconductors exhibit charge mobility values of up to 0.05 cm² V⁻¹ s⁻¹.     

A Thiophene Backbone Enables Two-Dimensional Poly(arylene vinylene)s with High Charge Carrier Mobility

Linear conjugated polymers have attracted significant attention in organic electronics in recent decades. However, despite intrachain π-delocalization, interchain hopping is their transport bottleneck. In contrast, two-dimensional (2D) conjugated polymers, as represented by 2D π-conjugated covalent organic frameworks (2D c-COFs), can provide multiple conjugated strands to enhance the delocalization of charge carriers in space. Herein, we demonstrate the first example of thiophene-based 2D poly(arylene vinylene)s (PAVs, 2DPAV-BDT-BT and 2DPAV-BDT-BP , BDT=benzodithiophene, BT=bithiophene, BP=biphenyl) via Knoevenagel polycondensation. Compared with 2DPAV-BDT-BP , the fully thiophene-based 2DPAV - BDT - BT exhibits enhanced planarity and π-delocalization with a small band gap (1.62 eV) and large electronic band dispersion, as revealed by the optical absorption and density functional calculations. Remarkably, temperature-dependent terahertz spectroscopy discloses a unique band-like transport and outstanding room-temperature charge mobility for 2DPAV-BDT-BT (65 cm² V⁻¹ s⁻¹), which far exceeds that of the linear PAVs, 2DPAV-BDT-BP , and the reported 2D c-COFs in the powder form. This work highlights the great potential of thiophene-based 2D PAVs as candidates for high-performance opto-electronics.     

High Compression-Induced Conductivity in a Layered Cu–Br Perovskite

We show that the onset pressure for appreciable conductivity in layered copper-halide perovskites can decrease by ca. 50 GPa upon replacement of Cl with Br. Layered Cu–Cl perovskites require pressures >50 GPa to show a conductivity of 10⁻⁴ S cm⁻¹, whereas here a Cu–Br congener, (EA)₂CuBr₄ (EA=ethylammonium), exhibits conductivity as high as 2×10⁻³ S cm⁻¹ at only 2.6 GPa, and 0.17 S cm⁻¹ at 59 GPa. Substitution of higher-energy Br 4p for Cl 3p orbitals lowers the charge-transfer band gap of the perovskite by 0.9 eV. This 1.7 eV band gap decreases to 0.3 eV at 65 GPa. High-pressure X-ray diffraction, optical absorption, and transport measurements, and density functional theory calculations allow us to track compression-induced structural and electronic changes. The notable enhancement of the Br perovskite's electronic response to pressure may be attributed to more diffuse Br valence orbitals relative to Cl orbitals. This work brings the compression-induced conductivity of Cu-halide perovskites to more technologically accessible pressures.     

Precision Graphene Nanoribbon Heterojunctions by Chain-Growth Polymerization

Graphene nanoribbons (GNRs) are considered promising candidates for next-generation nanoelectronics. In particular, GNR heterojunctions have received considerable attention due to their exotic topological electronic phases at the heterointerface. However, strategies for their precision synthesis remain at a nascent stage. Here, we report a novel chain-growth polymerization strategy that allows for constructing GNR heterojunction with N=9 armchair and chevron GNRs segments ( 9-AGNR/cGNR ). The synthesis involves a controlled Suzuki–Miyaura catalyst-transfer polymerization (SCTP) between 2-(6′-bromo-4,4′′-ditetradecyl-[1,1′:2′,1′′-terphenyl]-3′-yl) boronic ester ( M1 ) and 2-(7-bromo-9,12-diphenyl-10,11-bis(4-tetradecylphenyl)-triphenylene-2-yl) boronic ester ( M2 ), followed by the Scholl reaction of the obtained block copolymer ( poly-M1/M2 ) with controlled M_n (18 kDa) and narrow Đ (1.45). NMR and SEC analysis of poly-M1/M2 confirm the successful block copolymerization. The solution-mediated cyclodehydrogenation of poly-M1/M2 toward 9-AGNR/cGNR is unambiguously validated by FT-IR, Raman, and UV/Vis spectroscopies. Moreover, we also demonstrate the on-surface formation of pristine 9-AGNR/cGNR from the unsubstituted copolymer precursor, which is unambiguously characterized by scanning tunneling microscopy (STM).     

Large Nonlinear Optical Activity of a Near-infrared-absorbing Bithiophene-based Polymer with a Head-to-head Linkage

Although the production of near-infrared (NIR)-absorbing organic polymers with an excellent nonlinear optical (NLO) response is vital for various optoelectronic devices and photodynamic therapy, the molecular design and relevant photophysical investigation still remain challenging. In this work, large NLO activity is observed for an NIR-absorbing bithiophene-based polymer with a unique head-to-head linkage in the NIR region. The saturable absorption coefficient and modulation depth of the polymer are determined as ∼−3.5×10⁵ cm GW⁻¹ and ∼32.43%, respectively. Notably, the polymer exhibits an intrinsic nonlinear refraction index up to ∼−9.36 cm² GW⁻¹, which is six orders of magnitude larger than that of CS₂. The maximum molar-mass normalized two-photon absorption cross-section (σ₂/M) of this polymer can be up to ∼14 GM at 1200 nm. Femtosecond transient absorption measurements reveal significant spectral overlap between the 2PA and excited state absorption in the 1000–1400 nm wavelength range and an efficient triplet quantum yield of ∼36.7%. The results of this study imply that this NIR-absorbing polymer is promising for relevant applications.     

Band Gap of Atomically Precise Graphene Nanoribbons as a Function of Ribbon Length and Termination

We study the band gap of finite armchair graphene nanoribbons (7-AGNRs) on Au(111) through scanning tunneling microscopy/spectroscopy combined with density functional theory calculations. The band gap of 7-AGNRs with lengths of 8 nm and more is converged to within 50 meV of its bulk value of , while the band gap opens by several hundred meV in very short 7-AGNRs. We demonstrate that even an atomic defect, such as the addition of one hydrogen atom at the termini, has a significant effect – in this case, lowering the band gap. The effect can be captured in terms of a simple analytical model by introducing an effective “electronic length”.     

Yttrium Doped Copper (II) Oxide Hole Transport Material as Efficient Thin Film Transistor

This work reports development of yttrium doped copper oxide (Y−CuO) as a new hole transport material with supplemented optoelectronic character. The pure and Y-doped CuO thin films are developed through a solid-state method at 200 °C and recognized as high performance p-channel inorganic thin-film transistors (TFTs). CuO is formed by oxidative decomposition of copper acetylacetonate, yielding 100 nm thick and conductive (40.9 S cm⁻¹) compact films with a band gap of 2.47 eV and charge carrier density of ∼1.44×10¹⁹ cm⁻³. Yttrium doping generates denser films, Cu₂Y₂O₅ phase in the lattice, with a wide band gap of 2.63 eV. The electrical conductivity increases nine-fold on 2 % Y addition to CuO, and the carrier density increases to 2.97×10²¹ cm⁻³, the highest reported so far. The TFT devices perform remarkably with high field-effect mobility (μ_sat) of 3.45 cm² V⁻¹ s⁻¹ and 5.3 cm² V⁻¹ s⁻¹, and considerably high current-on/off ratios of 0.11×10⁴ and 9.21×10⁴, for CuO and Y−CuO films, respectively (at −1 V operating voltage). A very small width hysteresis, 0.01 V for CuO and 1.92 V for 1 % Y−CuO, depict good bias stability. Both the devices work in enhancement mode with stable output characteristics for multiple forward sweeps (5 to −60 V) at −1V_g.     

A Near‐Infrared Dye That Undergoes Multiple Interconversions through Acid–Base Equilibrium and Reversible Redox Processes

A near‐infrared (NIR) polymethine dye ( 1 ), consisting of a cyclohepta[1,2‐b ;4,3‐b′ ]dithiophene and two phenol moieties, was synthesized. This dye exhibited pH‐responsive changes in its photophysical properties due to a two‐step acid–base equilibrium that produced a protonated cation ( 1H⁺ ) and an anion ( 1⁻ ). While 1H⁺ showed an intense fluorescence in the red region of the visible spectrum, 1⁻ exhibited a strong absorption in the NIR region. The tropylium ion character in 1H⁺ induces high pK _a1 and pK _a2 values for 1 . Moreover, a stable radical ( 1^. ) was prepared, which showed a NIR absorption band with a maximum at circa 1600 nm. The cyclic voltammogram of 1^. revealed a two‐step reversible redox process that produced 1⁻ and the cation 1⁺ , which is different from 1H⁺ . These redox processes accompany drastic electrochromic changes in the vis–NIR region. Overall, 1 is susceptible to multiple interconversions between five forms, due to the multifaceted character of the cycloheptadithiophene skeleton.     

A Near-Infrared Dye That Undergoes Multiple Interconversions through Acid–Base Equilibrium and Reversible Redox Processes

A near-infrared (NIR) polymethine dye ( 1 ), consisting of a cyclohepta[1,2-b;4,3-b′]dithiophene and two phenol moieties, was synthesized. This dye exhibited pH-responsive changes in its photophysical properties due to a two-step acid–base equilibrium that produced a protonated cation ( 1H⁺ ) and an anion ( 1⁻ ). While 1H⁺ showed an intense fluorescence in the red region of the visible spectrum, 1⁻ exhibited a strong absorption in the NIR region. The tropylium ion character in 1H⁺ induces high pK_a1 and pK_a2 values for 1 . Moreover, a stable radical ( 1^. ) was prepared, which showed a NIR absorption band with a maximum at circa 1600 nm. The cyclic voltammogram of 1^. revealed a two-step reversible redox process that produced 1⁻ and the cation 1⁺ , which is different from 1H⁺ . These redox processes accompany drastic electrochromic changes in the vis–NIR region. Overall, 1 is susceptible to multiple interconversions between five forms, due to the multifaceted character of the cycloheptadithiophene skeleton.     

B←N-Incorporated Dibenzo-azaacene with Selective Near-Infrared Absorption and Visible Transparency

Organic compounds with selective near-infrared absorption and visible transparency are very desirable for fabrication of transparent/semitransparent optoelectronic devices. Herein, we develop a molecule with selective near-infrared absorption property, QBNA-O , in which four B←N units are incorporated to the core and two benzodioxin groups are introduced at the termini of the dibenzo-azaacene skeleton. QBNA-O exhibits a small optical gap of 1.39 eV due to the strong electron-donating benzodioxin groups and the strong electron-withdrawing B←N units. In toluene solution, QBNA-O shows a strong absorption peak at 856 nm with the full width at half maximum (FWHM) of only 41 nm as well as very weak absorption in the visible range from 380 nm to 760 nm. Thin films of QBNA-O exhibit the average visible transparency (AVT) of 78 % at the thickness of 205 nm and 90 % at the thickness of 45 nm. Solution-processed organic field-effect transistors (OFETs) of QBNA-O display ambipolar transporting behavior with the electron mobility of 0.52 cm² V⁻¹ s⁻¹ and the hole mobility of 0.013 cm² V⁻¹ s⁻¹ together with excellent air-stability. The selective NIR absorbing property and excellent charge transporting property imply that QBNA-O can be used to fabricate transparent organic optoelectronic devices.     

Dissociative Electron Attachment to Hexachlorobenzene

Gas phase molecules of hexachlorobenzene (C₆Cl₆) were investigated by means of dissociative electron attachment spectroscopy (DEAS). Three channels of molecular negative ions decay have been identified: abstraction of Cl⁻ and Cl₂⁻ as well as electron detachment (τ_a∼250 μs at 343 K). All three channels exhibit temperature dependence. The adiabatic electron affinity estimated using a simple but typically accurate Arrhenius model (EA_a=1.6–1.9 eV) turns out to be much higher than the quantum-chemical predictions (EA_a=0.9–1.0 eV). We discuss the possible reasons behind the observed discrepancy.     

Facile one pot synthesis of PbS nanosheets and their characterization

Metal-sulfides semiconductor nanosheets are talented entrant to be applied in electro-optic devices. Hence, the synthesis of PbS nanosheets is achieved in the current work using a simple route. The synthesized nanosheets were characterized by X-ray diffraction (XRD), FT-Raman, scanning electron microscope (SEM), UV-Visible, Photoluminescence (PL) and impedance spectroscopy techniques. XRD pattern and Raman spectrum confirms the formation of crystalline structure of PbS nanosheets. SEM study shows that the synthesized PbS is well defined nanosheets of <5 nm thicknesses. The absorption band edge is found to be remarkably blue shifted in nanosheets compare to bulk. The energy gap is calculated to be 1.16 eV which is about 3 times superior than the bulk value (0.41 eV). The enhancement of band gap indicates the occurrence of quantum confinement effect in PbS nanosheets. A strong violet emission band at ∼405 nm is observed in PL spectrum which is assigned to electrons transition from conduction-band edge to holes, ensnared at interstitial Pb²⁺ sites.     

An optical, EPR and electrical conductivity study of blue barium titanate, BaTiO3−δ

The electronic UV–VIS–NIR absorption spectra of single crystalline BaTiO_3−δ (BTO) are studied in the temperature range of 102–1173 K in pure oxygen and at conditions of moderate and strong reduction of the material. The strongly reduced crystals are of deep blue colour. The optical spectra of blue BTO are characterised by a strong absorption in the NIR region at around 7000 cm⁻¹, which is attributed to polaronic defects associated with the formation of Ti³⁺ in the material. This assumption is supported by fits of the spectra using polaronic line shape functions appropriate for disordered systems and also by the electrical conductivity of blue BTO which, in agreement with results from the optical spectra, exhibits an activation energy of 0.20 eV. The EPR spectra of moderately reduced BTO powders show an anisotropic g-factor, which is compatible with the optical spectrum. The temperature dependence of the band gap energy of BTO was found to be given as dE_g/dT = −7.21 × 10⁻⁴ eV/K.     

Rapid discrimination of Eurycoma longifolia extracts by Fourier transform infrared spectroscopy and two dimensional correlation infrared spectroscopy

Eurycoma longifolia is a herbal medicinal plant of South-East Asian origin, popularly recognized as ‘Tongkat Ali’. The root extracts have been used in indigenous traditional medicines for its unique antimalarial, anti-pyretic, antiulcer, cytotoxic and aphrodisiac properties. It is an important task that fast and effective analysis methods monitor the inherent qualities of traditional herbal medicines and its corresponding extracts products as a complicated mixture system. Owing to the unique fingerprint character and extensive applicability to test sample, infrared spectral method have been used in many research fields. In this paper, we use FT-IR, second derivative infrared spectroscopy and two-dimensional correlation infrared spectroscopy (2D-IR) step by step to analyze E. longifolia and its different extracts (extracted by hexane, ethyl acetate, dichloromethane and methanol in turn). The findings indicated that FT-IR and 2D-IR can provide many holistic variation rules of chemical constituents. The structural information of the samples indicated that E. longifolia and its extracts contain a large amount of quassinoids, since some characteristic absorption peaks of quassinoids, such as ∼1700 cm⁻¹, ∼1670 cm⁻¹, ∼1600 cm⁻¹,∼1500 cm⁻¹, and ∼1270 cm⁻¹ can be detected. This method, having its high resolution and excellent macroscopic fingerprint features, can not only supply lots of structural information of main components in the complicated system, but also can differentiate the tiny differences between the similar systems according to the macro-fringerprint characters. This method is highly rapid, effective, accurate and well repetitive for pharmaceutical research.     

A p‐Quinodimethane‐Bridged Porphyrin Dimer

A p‐quinodimethane (p‐QDM)‐bridged porphyrin dimer 1 has been prepared for the first time. An unexpected Michael addition reaction took place when we attempted to synthesize compound 1 by reaction of the cross‐conjugated keto‐linked porphyrin dimers 8 a and 8 b with alkynyl/aryl Grignard reagents. Alternatively, compound 1 could be successfully prepared by intramolecular Friedel–Crafts alkylation of the diol‐linked porphyrin dimer 14 with concomitant oxidation in air. Compound 1 shows intense one‐photon absorption (OPA, λ_max=955 nm, ε=45400 M ^?1 cm^?1) and a large two‐photon absorption (TPA) cross‐section (σ⁽²⁾_max=2080 GM at 1800 nm) in the near‐infrared (NIR) region due to its extended π‐conjugation and quinoidal character. It also exhibits a short singlet excited‐state lifetime of 25 ps. The cyclic voltammogram of 1 displays multiple redox waves with a small electrochemical energy gap of 0.86 eV. The ground‐state geometry, electronic structure, and optical properties of 1 have been further studied by density functional theory (DFT) calculations and compared with those of the keto‐linked dimer 8 b . This research has revealed that incorporation of a p‐QDM unit into the porphyrin framework had a significant impact on its optical and electronic properties, leading to a novel NIR OPA and TPA chromophore.     

Rate coefficients for the reactions of OH with butanols from 298 K to temperatures relevant for low-temperature combustion

Rate coefficients for the reactions of OH with n, s, and iso-butanol have been measured over the temperature range 298 to ∼650 K. The rate coefficients display significant curvature over this temperature range and bridge the gap between previous low-temperature measurements with a negative temperature dependence and higher temperature shock tube measurements that have a positive temperature dependence. In combination with literature data, the following parameterizations are recommended: k_{1,OH + n-butanol}(T) = (3.8 ± 10.4) × 10⁻¹⁹T^{2.48 ± 0.37}exp ((840 ± 161)/T) cm³ molecule⁻¹ s⁻¹ k_{2,OH + s-butanol}(T) = (3.5 ± 3.0) × 10⁻²⁰T^{2.76 ± 0.12}exp ((1085 ± 55)/T) cm³ molecule⁻¹ s⁻¹ k_{3,OH + i-butanol}(T) = (5.1 ± 5.3) × 10⁻²⁰T^{2.72 ± 0.14}exp ((1059 ± 66)/T) cm³ molecule⁻¹ s⁻¹ k_{4,OH + t-butanol}(T) = (8.8 ± 10.4) × 10⁻²²T^{3.24 ± 0.15}exp ((711 ± 83)/T) cm³ molecule⁻¹ s⁻¹ Comparison of the current data with the higher shock tube measurements suggests that at temperatures of ∼1000 K, the OH yields, primarily from decomposition of β-hydroxyperoxy radicals, are ∼0.3 (n-butanol), ∼0.3 (s-butanol) and ∼0.2 (iso-butanol) with β-hydroxyperoxy decompositions generating OH, and a butene as the main products. The data suggest that decomposition of β-hydroxyperoxy radicals predominantly occurs via OH elimination.