Thioxobimanes.

Dioxobimanes, colloquially known as bimanes, are a well-established family of N-heterobicyclic compounds that share a characteristic core structure, 1,5-diazabicyclo[3.3.0]octadienedione, bearing two endocyclic carbonyl groups. By sequentially thionating these carbonyls in the syn and anti isomers of the known (Me,Me)dioxobimane, we were able to synthesize a series of thioxobimanes, representing the first heavy-chalcogenide bimane variants. These new compounds were extensively characterized spectroscopically and crystallographically, and their aromaticity was probed computationally. Their potential role as ligands for transition metals was demonstrated by synthesizing a representative gold(I)-thioxobimane complex.

Multicomponent Reaction Based Tolyl-substituted and Pyrene-Pyridine Conjugated Isomeric Ratiometric Fluorescent Probes: A Comparative Investigation of Photophysical and Hg(II)-Sensing Behaviors.

Herein, the synthesis of pyrene conjugated 2,6-di-ortho-tolylpyridine and 2,6-di-para-tolylpyridine structural isomers were achieved efficiently through multicomponent Chichibabin pyridine synthesis reaction. The DFT, TD-DFT and experimental investigations were carried out to investigate the photophysical behaviors of the synthesized novel pyrene-pyridine based isomeric probes. Our studies revealed that, due to the continuous conjugation of the pyrene, pyridine and tolyl moieties, the dihedral angles of the trisubstituents on the central pyridine moiety significantly influences the photophysical properties of the synthesized novel pyrene based fluorescent probes. Further, we have comparatively investigated the sensing behaviors of the synthesized tolyl-substituted isomeric ratiometric fluorescent probes with metal ions, our studies reveals that both the ortho and para tolyl ratiometric fluorescent probes have distinct photoemissive properties in selectively sensing of Hg2+ ions. Our studies indicates that, the para-tolyl substituted isomer displays more red-shift in wavelength of emission band compared to its ortho isomer analogue during ratiometric fluorescent specific detection of Hg2+ ions.

TICT, and Deep-Blue Electroluminescence from Acceptor-Donor-Acceptor Molecules.

Donor-acceptor (D-A) materials based on butterfly-shaped molecules could inhibit exciton-migration-induced quenching due to molecular twist. To explore this attribute towards beneficial photophysical properties, three novel bipolar acceptor-donor-acceptor (A-D-A) molecules with triphenyl triazine end capping along with substitution ortho to the Tröger's base (TB) scaffold varying from H, Me, and F were explored. The installation of H/Me/F imparted an electron push-pull effect with concomitant maneuvering of photophysical properties. On increasing solvent polarity, a remarkable bathochromic shift with a significant decrease in emission efficiency was observed due to the twisted intramolecular charge transfer state (TICT). Emission enhancement in the ethylene glycol-water mixture and diminution in the THF-water mixture further confirmed the existence of TICT states in these TBs. The torsional dynamics in the excited state were also evidenced by the time-dependent density-functional theory (TD-DFT) calculations. Owing to the butterfly architecture of the TB that suppressed TICT, TB-Trzs exhibited a significant blue shift, accompanied by a favorable quantum yield in the solid state. Among the three compounds, Me-TB-Trz exhibited deep-blue photoluminescence and was explored as a dopant in organic light-emitting diodes (OLEDs) to obtain deep-blue electroluminescence of brightness 4128 cdm-2 and CIE coordinates of (0.16, 0.09).

Art of Cross-Linking In Situ Bulk Perovskites for Efficient and Stable Photovoltaics.

Perovskites are hybrid materials containing templating organic linkers and inorganic halides with efficiencies that have superseded the efficiency of silicon-based photovoltaic devices (PVs) in a very short period of 10 years. Nevertheless, low ambient stability due to traps and ion migration caused hysteresis to remain the bottlenecks on the way to achieving higher operational stability with bulk perovskite-based PVs. In this context, herein we highlight the prospects of in situ cross-linking of linkers within the perovskite lattice either mediated by thermal means or attained photochemically that can maneuver the ambient as well as operational stability for enhanced power conversion efficiency for PV applications or could improve the conductivity of this hybrid semiconductor. Additionally, some important studies of additive engineering via in situ cross-linking that can affect the structure of perovskite in addition to defect passivation to endow ambient environment stability are highlighted herein.

Construction of a 3D Metal-Organic Framework and Its Composite for Water Remediation via Selective Adsorption and Photocatalytic Degradation of Hazardous Dye.

In this work, a new bimetallic Na(I)-Zn(II) metal-organic framework (MOF), formulated as [Na2Zn3(btc)2(µ-HCOO)2(µ-H2O)8] n (1) (H3btc = benzene tricarboxylic acid), and its composite (ZnO@1) have been successfully synthesized using solvothermal and mechanochemical solid grinding methods. 1 and ZnO@1 were characterized by diffraction [single-crystal X-ray diffraction (XRD) and powder XRD], spectroscopic (ultraviolet-visible diffuse reflectance spectroscopy and Fourier transform infrared spectroscopy), microscopic (transmission electron microscopy), and thermal (thermogravimetric analysis) methods. The surface area and porosity of 1 were determined using a Brunauer-Emmett-Teller analyzer. Single-crystal diffraction of 1 confirms that Na1 and Zn2 have octahedral coordination environments, whereas Zn1 has a tetrahedral coordination geometry. Topological simplification of 1 shows a 3,6-connected kgd net. Na(I)-Zn(II) MOF (1) is crystallized with slight porosity and exhibits good tendency toward the encapsulation of zinc oxide nanoparticles (ZnO NPs). The photocatalytic behaviors of 1 and its composite (ZnO@1) were investigated over MB dye under sunlight illumination with promising degradation efficiencies of 93.69% for 1 and 97.53% for ZnO@1 in 80 min.

High Stability Bilayered Perovskites through Crystallization Driven Self-Assembly.

In this manuscript we reveal the formation of bilayered hybrid perovskites of a new lower dimensional perovskite family, (CHMA)2(MA)n-1PbnI3 with n = 1-5, with high ambient stability via its crystallization driven self-assembly process. The spun-coated perovskite solution tends to crystallize and undergo phase separation during annealing, resulting in the formation of 2D/3D bilayered hybrid perovskites. Remarkably, this 2D/3D hybrid perovskites possess striking moisture resistance and displays high ambient stability up to 65 days. The bilayered approach in combining 3D and 2D perovskites could lead to a new era of perovskite research for high-efficiency photovoltaics with outstanding stability, with the 3D perovskite providing excellent electronic properties while the 2D perovskite endows it moisture stability.

Broadband-Emitting 2 D Hybrid Organic-Inorganic Perovskite Based on Cyclohexane-bis(methylamonium) Cation.

A new broadband-emitting 2 D hybrid organic-inorganic perovskite (CyBMA)PbBr4 based on highly flexible cis-1,3-bis(methylaminohydrobromide)cyclohexane (CyBMABr) core has been designed, synthesized, and investigated, highlighting the effects of stereoisomerism of the templating cation on the formation and properties of the resulting perovskite. The new 2 D material has high exciton binding energy of 340 meV and a broad emission spanning from 380 to 750 nm, incorporating a prominent excitonic band and a less intense broad peak at room temperature. Significant changes in the photoluminescence (PL) spectrum were observed at lower temperatures, showing remarkable enhancement in the intensity of the broadband at the cost of excitonic emission. Temperature-dependent PL mapping indicates the effective role of only a narrow band of excitonic absorption in the generation of the active channel for emission. Based on the evidences obtained from the photophysical investigations, we attributed the evolution of the broad B-band of (CyBMA)PbBr4 to excitonic self-trapped states.

Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites.

Ultrafast spin manipulation for opto-spin logic applications requires material systems that have strong spin-selective light-matter interaction. Conventional inorganic semiconductor nanostructures [for example, epitaxial II to VI quantum dots and III to V multiple quantum wells (MQWs)] are considered forerunners but encounter challenges such as lattice matching and cryogenic cooling requirements. Two-dimensional halide perovskite semiconductors, combining intrinsic tunable MQW structures and large oscillator strengths with facile solution processability, can offer breakthroughs in this area. We demonstrate novel room-temperature, strong ultrafast spin-selective optical Stark effect in solution-processed (C6H4FC2H4NH3)2PbI4 perovskite thin films. Exciton spin states are selectively tuned by ~6.3 meV using circularly polarized optical pulses without any external photonic cavity (that is, corresponding to a Rabi energy of ~55 meV and equivalent to applying a 70 T magnetic field), which is much larger than any conventional system. The facile halide and organic replacement in these perovskites affords control of the dielectric confinement and thus presents a straightforward strategy for tuning light-matter coupling strength.

Amorphous host materials based on Tröger's base scaffold for application in phosphorescent organic light-emitting diodes.

Tröger's bases (TBs) functionalized with carbazoles (TB-Czs) and phosphine oxides (TB-POs) were designed and synthesized as host materials for application in phosphorescent organic light-emitting diodes. The TB scaffold is shown to impart thermal stability with high Tg values (171-211 °C) as well as high triplet energies in the range of 2.9-3.0 eV. With a limited experimentation of the devices, it is shown that the TBs doped with a green phosphor, namely, Ir(ppy)3, permit impressive external efficiencies on the order of ca. 16% with a high brightness of ca. 3000-4000 cd/m2. Better device performance results are demonstrated by a small structural manipulation of the TB scaffold involving substitution of methyl groups in the core scaffold.