Synthesis,structural analysis,spectral investigations,and DFT calculations of 1‐(3‐amino‐4‐thia‐1,2‐diazaspiro[4.11]hexadec‐2‐en‐1‐yl)ethan‐1‐one

1‐(3‐amino‐4‐thia‐1,2‐diazaspiro[4.11]hexadec‐2‐en‐1‐yl)ethan‐1‐one was synthesized and experimentally characterized by using FT‐IR, ¹H NMR, ¹³C NMR, and UV–Vis spectroscopy. The structure of the compound was confirmed by single‐crystal X‐ray diffraction. In the crystal structure, the molecules are linked by pairs of N‐H⋯N hydrogen bonds, forming centrosymmetric dimers with the graph‐set motif. The water molecule also plays an important role in the stabilization of the crystal structure, bridging the dimers to form a two‐dimensional supramolecular network. The molecular geometry, frontier molecular orbitals, vibrational frequencies, electronic properties, and molecular electrostatic potential were calculated using density functional theory (DFT) with the B3LYP/6‐311G(d,p) basis set. Geometric parameters, vibrational assignments, and electronic properties such as calculated energies, excitation energies, and oscillator strengths were compared with the experimental data, and it was seen that the theoretical results support the experimental parameters.     

One‐pot,Multicomponent Cascade Reaction for the Synthesis of Various Aralkyl/alkylthio‐3,5‐dimethyl‐1H‐pyrazolyl‐4H‐1,2,4‐triazol‐4‐amine and Their Docking Studies

A facile and simple one‐pot procedure for the synthesis of various aralkyl/alkylthio‐3,5‐dimethyl‐1H‐pyrazolyl‐4H‐1,2,4‐triazol‐4‐amines has been described via a multicomponent reaction of 4‐amino‐5‐hydrazinyl‐4H‐1,2,4‐triazole‐3‐thiol, acetylacetone, and various aryl/alkyl halides in good yields. All the newly synthesized compounds were characterized by using analytical and spectral studies. Our in silico studies confirmed that 4e , 4f , 4g , and 4j have the best inhibition activity among the synthesized compounds with a high selective index against the Tubulin protein and showed best interactions with receptor structure. The present study provides a novel series of compounds with a promising inhibitor to prevent on Tubulin protein.     

Facile synthesis of multi‐functional 1,3,4‐thiadiazine derivatives bearing phthalazine,pyridazine, and pyrido‐pyridazine moieties

A series of novel, multifunctional 1,3,4‐thiadiazine derivatives bearing phthalazines, pyridazines and pyrido‐pyridazines ( 9–13 ) have been synthesized via the multicomponent reaction of (3‐(2‐bromo‐2‐[2‐chloropyrimidin‐4‐yl]acetyl)‐2‐chlorophenyl)‐2,6‐dichloro benzene‐sulfonamide with thiocarbohydrazide and various anhydrides. The reactions were performed by refluxing the components in mixed ethanol/acetic acid to afford the corresponding products in good to excellent yields. All the synthesized compounds were characterized by analytical and spectral studies. The developed method features short reaction time, simple work‐up without chromatographic separation, and a broad range of substrate applicability.     

Host-Guest Interactions between N,N＇-Bis（ferrocenylmethyl- ene）-Diaminobutane and Benzenetetracarboxylic Dianhydride Bridged Bis（β-cyclodextrin）s

A novel water soluble ditopic guest, the quaternary ammonium salt of N,N＇-bis（ferrocenylmethylene）-diaminobutane （1）, and a known water soluble ditopic host, benzenetetracarboxylic dianhydride bridged bis（β-cyclodextrin）s （2）, have been synthesized and characterized. ^1H NMR spectra and cyclic voltammogram （CV） studies revealed the host-guest interactions between them in aqueous solution. The supramolecular interaction also exists in solid state as confirmed by the studies of the solid samples, which were obtained by frozen-drying the solution sampies, using FTIR spectroscopy and differential scanning calorimetry （DSC） techniques. TEM measurement demonstrated that wire-shaped supramolecular aggregates exist in the aqueous solution of the two compounds. The lengths of the aggregates could reach micrometers.     

Low‐bandgap donor–acceptor copolymers with 4,6‐bis(3′‐(2‐ethylhexyl)thien‐2′‐yl)thieno[3,4‐c][1,2,5]thiadiazole: synthesis,optical, electrochemical,and photovoltaic properties

Two new low‐bandgap alternating copolymers (CEHTF and CEHTP) consisting of 4,6‐bis(3′‐(2‐ethylhexyl)thien‐2′‐yl)thieno[3,4‐c][1,2,5] thiadiazole and 9,9‐bis(2‐ethylhexyl)fluorene or 2,5‐bis(isopentyloxy)benzene were synthesized by Suzuki coupling reaction of corresponding comonomers. Their optical, electrochemical, and photovoltaic (PV) properties were studied and are reported. Both the copolymers exhibited long‐wavelength absorption covering the whole visible spectral region, which is in CEHTP thin films extended up to near infrared region, ambipolar redox properties, and electrochromism. High‐electron affinities and low‐optical bandgap values, 1.37 and 1.15 eV, were determined for CEHTF and CEHTP, respectively. PV devices with bulk heterojunction made of blends of copolymers and fullerene derivative [6,6]‐phenyl‐C⁶¹‐butyric acid methyl ester ([60]PCBM) were prepared and characterized. Effects of intramolecular charge transfer strength and side‐chain nature and length on photophysical properties are discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Design and Synthesis of 2,5‐Disubstituted‐1,3,4‐Oxadiazole Hybrids Bearing Pyridine and 1,2,3‐Triazole Pharmacophores

A novel series of 2,5‐disubstituted‐1,3,4‐oxadiazoles decorated with two biodynamic moieties pyridine and 1,2,3‐triazole have been successfully synthesized in good yields under mild reaction conditions. The synthesized compounds are valuable for biological activity exploration since three biodynamic moieties are covalently linked together in a single molecular framework. All the synthesized compounds were fully characterized by their detailed spectral studies IR, ¹HNMR, ¹³C NMR and Mass.     

Synthesis,characterization, and electroluminescence of fluorene and carbazole‐based blue light‐emitting polymers with different noncoplanar molecular architectures

In order to investigate the explicit optoelectronic variations of the photoluminescent polymer with sterically hindered side chains, three novel alternate polymers (P0, P1, and P2) based on fluorene and carbazole moieties were successfully synthesized through Suzuki coupling reaction. The molecular structures of the polymers were fully characterized by ¹H‐NMR, ¹³C‐NMR, elemental analysis, and gel permeation chromatograph, respectively. The photophysical properties, thermal stability, and energy band gaps of polymers P0, P1, and P2 were further examined through UV–vis absorption, photoluminescent spectra, differential scanning calorimetry, thermogravimetric analysis, and cyclic voltammetry. The experimental results indicated that the polymers took on wide band gaps of about 3.50 eV with deep blue emission in thin solid films. These polymers were found to show a high thermal stability with decomposition temperatures at 5% weight loss of the compounds in the range of 353–416 °C. Blue light‐emitting electroluminescent devices of the most branched polymer P2 with highest light‐emitting efficiency as emitting layers were characterized, which showed obviously improved spectral stabilities with respect to the parent polyfluorene materials. In conclusion, we have established an effective method to improve the spectral stabilities of polyfluorene material by synthesizing the zigzag‐shaped copolymer of fluorene and carbazole with sterically hindered pendant moieties of different molecular sizes. Copyright © 2014 John Wiley & Sons, Ltd.     

Mechanochromic Behavior of Aryl‐Substituted Buta‐1,3‐Diene Derivatives with Aggregation Enhanced Emission

Three tetra‐aryl substituted 1,3‐butadiene derivatives with aggregation enhanced emission (AEE) and mechanochromic fluorescence behavior have been rationally designed and synthesized. The results suggest an effective design strategy for developing diverse materials with aggregation induced emission (AIE) and significant mechanochromic performance by employing D ‐π‐A structures with large dipole moments.     

5,6,12,13‐Tetraazaperopyrenes as Unique Photonic and Mechanochromic Fluorophores

5,6,12,13‐Tetraazaperopyrenes with different number of tert‐butyl groups (c‐TAPP‐T, c‐TAPP‐H) were synthesized, via four‐fold Bischler–Napieralski cyclization as the key step. As deduced from the single‐crystal structures and optical properties, N‐doping and substitution type allow for a precise control of intermolecular interactions. Compared to the reported 1,3,8,10‐tetraazaperopyrenes, significantly different packing modes were found in 5,6,12,13‐tetraazaperopyrenes. Going from c‐TAPP‐T to c‐TAPP‐H, two additional tert‐butyl groups lead to different preferential growth directions, affording 1D and 2D microcrystals, respectively. Most importantly, both microcrystals exhibit excellent optical waveguide properties with extraordinarily low loss coefficients and unique polarization features. Although c‐TAPP‐H possesses a rigid and planar core, its crystals display an exceptional mechanochromic fluorescence, which, again, depends on the mode of molecular packing.     

Synthesis and Pharmacological Evaluation of a Novel Series of 2‐((2‐Aryl thiazol‐4‐yl)methyl)‐5‐(alkyl/alkylnitrile thio)‐1,3,4‐oxadiazole Derivatives as Possible Antifungal Agents

In the present investigation, a novel series of 2‐[(2‐arylthiazol‐4‐yl)methyl]‐5‐(alkyl/alkylnitrile thio)‐1,3,4‐oxadiazole derivatives were synthesized by cyclo‐condensation of 2‐(2‐substituted thiazol‐4‐yl)aceto hydrazide with carbon disulfide followed by S‐alkylation with alkyl halide in dry acetone. All the newly synthesized compounds were characterized by spectral (IR, ¹H NMR, ¹³C NMR, mass, and elemental analysis) methods. The title compounds were screened for in vitro antifungal activity and most of the synthesized compounds show moderate to good antifungal activity.     

Indium trichloride–catalyzed synthesis of some novel 2,2′‐(N,N′‐diarylamino)‐ 4,4′‐diaryl‐5,5′‐arylidenebisthiazoles and their insecticidal activity

A series of novel 2,2′‐(N,N′‐diarylamino)‐4,4′‐diaryl‐5,5′‐arylidene‐bisthiazoles 2 were rapidly and smoothly prepared in good yields by using non conventional techniques i.e. microwave or ultrasonic irradiation, through indium trichloride catalyzed electrophilic substitution reaction of 2‐(N‐arylamino)‐4‐arylthiazoles 1 with various arylaldehydes. All the synthesized compounds were characterized on the basis of their elemental analyses and spectral data (IR, PMR and Mass). The synthesized compounds were also evaluated for their insecticidal activity against Helicoverpa armigera and gave promising results. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:224–231, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20537     

Board‐like Fused‐Thiophene Liquid Crystals and their Benzene Analogs: Facile Synthesis,Self‐Assembly,p‐Type Semiconductivity,and Photoluminescence

Fused‐thiophene discotic liquid crystals were designed and easily synthesized by Suzuki coupling and FeCl₃ oxidized tandem cyclodehydrogenation reactions, including homo‐ and cross‐coupling reactions. The resulting hexagonal and rectangular columnar mesomorphic supramolecular structures formed were characterized by polarizing optical microscopy, differential scanning calorimetry, and small‐angle X‐ray scattering. The charge carrier transport properties in the mesophases of two of the synthesized fused‐thiophene discogens were measured by transient photocurrent time‐of‐flight (TOF) technique, revealing fast hole transport values in the range of 10^?3 to 10^?2 cm² V^?1 s^?1, thus demonstrating potential applications in electronic devices. The luminescent sanidic mesogens, with different extended π‐conjugated systems, also emit blue, green, or red light, with absolute photoluminescent quantum yields as high as 18 %.     

Synthesis,Characterization, Self‐Assembly,Gelation, Morphology and Computational Studies of Alkynylgold(III) Complexes of 2,6‐Bis(benzimidazol‐2′‐yl)pyridine Derivatives

A novel class of alkynylgold(III) complexes of the dianionic ligands derived from 2,6‐bis(benzimidazol‐2′‐yl)pyridine (H₂bzimpy) derivatives has been synthesized and characterized. The structure of one of the complexes has also been determined by X‐ray crystallography. Electronic absorption studies showed low‐energy absorption bands at 378–466 nm, which are tentatively assigned as metal‐perturbed π–π* intraligand transitions of the bzimpy^2? ligands. A computational study has been performed to provide further insights into the nature of the electronic transitions for this class of complexes. One of the complexes has been found to show gelation properties, driven by π–π and hydrophobic–hydrophobic interactions. This complex exhibited concentration‐ and temperature‐dependent ¹H NMR spectra. The morphology of the gel has been characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM).     

NLOphoric Triphenylamine Derived Donor‐π‐Acceptor‐π‐Donor Based Colorants: Synthesis,Spectroscopic, Density Functional Theory and Z‐scan Studies

Three Donor‐π‐Acceptor‐π‐Donor type styryl dyes ( 5a‐c ) with different secondary donors are synthesized and characterized to study their nonlinear and linear optical properties. The structure–property relationships of the dyes are described in the light of systematic photophysical and theoretical investigations. The photophysical characteristics of 5a‐c are influenced by the polarity of the medium, with an appreciable bathochromic shift in emission ( 5b = 81 nm) and large Stoke shifts ( 5b = 104–173 nm) in polar solvents. 5a‐c showed intramolecular charge transfer characteristics recognized with the help of emission solvatochromism, solvent polarity graphs, natural bond orbital analysis and HOMO–LUMO energy difference. The optimized geometry and frontier molecular orbitals reveal that the electron donation takes place from secondary donors and not from a fixed donor (triphenylamine) which is more twisted. The nonlinear optical properties obtained using solvent induced spectral shift and computational methods are found within the limiting values. Z‐scan results reveal saturable kind of behavior for 5a , 5b and 5c , whereas 5a and 5b show reverse saturable kind of behavior in acetone and ethanol and hence give optical limiting values. The two‐photon absorption cross section described by two‐level approximation is highest for 5b (251–300 GM).     

2‐Pyrazolin‐5‐One‐Based Heterocycles: Synthesis and Characterization

A novel series of pyrazoline and thiazole derivatives incorporating 2‐pyrazolin‐5‐one moiety were synthesized starting from α,β‐unsaturated ketones under the effect of hydrazine derivatives and thiosemicarbazide. The obtained pyrazolines 4a , 4b were treated with different reagents to afford N‐substituted pyrazolines 5a , 5b , 6a , 6b , 7a , 7b , 8a , 8b . N‐Thiocarbamoyl pyrazolines 12a , 12b were cyclized using phenacyl bromide, 2,3‐dichloroquinoxaline, and monochloroacetic acid afforded the novel pyrazolinyl thiazoles 13a , 13b , 14a , 14b , 15a , 15b , 16a , 16b , 16c , 16d , 16e , 16f . The newly synthesized compounds were characterized by analytical and spectral data.     

Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.     

6,7‐Bismethoxy‐2,11‐dihydroxytetraphenylene Derived Macrocycles: Synthesis,Structures, and Complexation with Fullerenes

6,7‐Bismethoxy‐2,11‐dihydroxytetraphenylene ( 1 ), a novel building block of tetraphenylene‐derived macrocycles, was synthesized via palladium‐catalyzed cross‐coupling reactions and characterized by X‐ray diffraction. The relevant macrocyclic hosts derived from 1 have well‐defined structures with fixed conformations both in solution and solid state. They showed efficient and unique properties toward complexation with fullerenes C₆₀ and C₇₀ in toluene.     

β‐Functionalized Push–Pull opp‐Dibenzoporphyrins as Sensitizers for Dye‐Sensitized Solar Cells

A novel class of β‐functionalized push–pull zinc opp ‐dibenzoporphyrins were designed, synthesized, and utilized as sensitizers for dye‐sensitized solar cells. Spectral, electrochemical, and computational studies were systematically performed to evaluate their spectral coverage, redox behavior, and electronic structures. These porphyrins displayed much broader spectral coverage and more facile oxidation upon extension of the π conjugation. Free‐energy calculations and femtosecond transient absorption studies (charge injection rate in the range of 10¹¹ s⁻¹) suggested efficient charge injection from the excited singlet state of the porphyrin to the conduction band of TiO₂. The power conversion efficiency (η ) of YH3 bearing acrylic acid linkers (η =5.9 %) was close to that of the best ruthenium dye N719 (η =7.4 %) under similar conditions. The superior photovoltaic performance of YH3 was attributed to its higher light‐harvesting ability and more favorable electron injection and collection, as supported by electrochemical impedance spectral studies. This work demonstrates the exceptional potential of benzoporphyrins as sensitizers for dye‐sensitized solar cells.     

Syntheses and Crystal Structures of Copper(II) and Silver Complexes with 5‐Methyl‐1‐(4‐Methylphenyl)‐1,2,3‐Triazol‐4‐Carboxylic Acid

Two novel complexes [Cu L ₂(MeOH)] ( 1 )and [Ag₂ L (H L )₂(MeOH)] ( 2 ) ( L = 5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐carboxylic acid) were synthesized and characterized by elemental analysis, IR and X‐ray diffraction. Complex 1 is a mononuclear structure; the molecules were assembled into an infinite 2–D supramolecular by the C–H···O weak interactions. Complex 2 is a centrosymmetric dinuclear structure with bis(unidentate) carboxylato co‐ordination mode, and the molecules were assembled into 2–D layers by C–H···O and O–H···O weak interactions.     

Synthesis and characterization of the novel l‐(substituted phenoxy/phenyl)‐2‐phospholene and phospholane 1‐oxide derivatives

The synthesis of the novel 1‐(substituted phenoxy/phenyl)‐2‐phospholene and phospholane 1‐oxide derivatives, which are analogs of sugars having a phosphorus atom in place of the ring oxygen of normal sugars, is described. All of the synthesized derivatives are structurally characterized by multi nuclear NMR, mass, and IR spectral data, elemental and X‐ray crystallographic analyses.