Donor–acceptor perylenediimide–ferrocene conjugates: synthesis,photophysical, and electrochemical properties

Donor–acceptor, perylenediimide–ferrocene conjugates have been synthesized by Suzuki, and Sonogashira coupling reactions. The photophysical and electrochemical properties of these conjugates are discussed. It has been shown that fluorescence as well as the electron affinity of the perylenediimide can be tuned by attaching the appropriate ferrocenyl derivatives.     

Synthesis of benzohetero[3, 2-a]pyrimidines using cyclic β-keto lactone as a building block

Abstract  

A novel method for the synthesis of 3-(2-substituted ethyl)-2-methylbenzohetero[3,2-a]pyrimidines in high yield (80–85%) was achieved, which involves a dihydrofuranone intermediate, readily obtained from β-ketolactone to 2-aminobenzoheterocycles. The major advantage of the methodology is the high yield and product purity.     

High Bio-Content Thermoplastic Polyurethanes from Azelaic Acid

To realize the commercialization of sustainable materials, new polymers must be generated and systematically evaluated for material characteristics and end-of-life treatment. Polyester polyols made from renewable monomers have found limited adoption in thermoplastic polyurethane (TPU) applications, and their broad adoption in manufacturing may be possible with a more detailed understanding of their structure and properties. To this end, we prepared a series of bio-based crystalline and amorphous polyester polyols utilizing azelaic acid and varying branched or non-branched diols. The prepared polyols showed viscosities in the range of 504–781 cP at 70 °C, with resulting TPUs that displayed excellent thermal and mechanical properties. TPUs prepared from crystalline azelate polyester polyol exhibited excellent mechanical properties compared to TPUs prepared from amorphous polyols. These were used to demonstrate prototype products, such as watch bands and cup-shaped forms. Importantly, the prepared TPUs had up to 85% bio-carbon content. Studies such as these will be important for the development of renewable materials that display mechanical properties suitable for commercially viable, sustainable products.     

β-Functionalized ethylchalcogenolate complexes of lead(II): Synthesis, structures and their conversion into lead chalcogenide nanoparticles

The reactions of Pb(OAc)₂·3H₂O with NaER yield homoleptic colorless to yellow complexes of composition, [Pb(ER)₂] (ER = SCH₂CH₂NMe₂ (1), SeCH₂CH₂NMe₂ (2) and SeCH₂CH₂COOMe (3)). These complexes were characterized by elemental analyses, UV–Vis and ¹H NMR data. Molecular structures of [Pb(ECH₂CH₂NMe₂)₂] (E = S or Se) have been established by single crystal X-ray diffraction analyses. These molecules have a distorted trigonal bipyramidal configuration around lead with the nitrogen atoms of the chelating chalcogenolate ligands occupying the axial positions. Thermal behavior of these complexes was studied by TG analysis. Pyrolysis in a furnace or in HDA (hexadecylamine) gave PbE nanoparticles which were characterized by UV–Vis, photoluminescence, XRD, EDAX, and TEM measurements.     

Group 12 metal monoselenocarboxylates: synthesis, characterization, structure and their transformation to metal selenide (MSe; M = Zn, Cd, Hg) nanoparticles

Reactions of [MCl2(tmeda)] with potassium salts of monoselenocarboxylic acids gave complexes of the general formula [M(SeCOR)2(tmeda)] (M = Zn, Cd; R = Ph, Tol; Tol = C6H4-p-CH3; tmeda = Me2NCH2CH2NMe2). The analogous mercury complexes were unstable at room temperature and afforded HgSe nanoparticles during the course of reaction. All the complexes were characterized by elemental analysis, IR, UV-vis, NMR (1H, 13C, 77Se, 113Cd) data. The X-ray structural analysis of [Cd(SeCOPh)2(tmeda)] revealed that the complex is a discrete monomer having an approximate tetrahedral coordination environment around the central metal atom with monodentate (Se-bonded) selenocarboxylates. Thermal behavior of these complexes was studied by TG analysis. Pyrolysis in a furnace or in HDA (hexadecylamine) gave MSe nanoparticles, which were characterized by XRD, EDAX, SEM and absorption spectroscopy.     

Synthesis and characterization of novel 2-(1-benzyl-3-[4-fluorophenyl]-1H-pyrazol-4-yl)-7-fluoro-4H-chromen-4-one derivatives

Novel 1-benzyl-3-(4-fluorophenyl)-1H-pyrazole-4-carbaldehydes 3a to 3e were synthesized via Vilsmeier-Haack reaction of the appropriate 1-benzyl-2-(1-(4-fluorophenyl)ethylidene)hydrazines, derived from 4-fluoroacetophenone 1 with substituted 2-benzylhydrazines 2a to 2e . The base catalyzed condensation of 1-benzyl-3-(4-fluorophenyl)-1H-pyrazole-4-carbaldehydes 3a to 3e with 1-(4-fluoro-2-hydroxyphenyl)ethanone 4 gave (E)-3-(1-benzyl-3-(4-fluorophenyl)-1H-pyrazol-4-yl)-1-(4-fluoro-2-hydroxyphenyl)prop-2-en-1-ones 5a to 5e . On cyclization with dimethyl sulfoxide (DMSO)/I₂, compounds 5a to 5e gave 2-(1-benzyl-3-(4-fluorophenyl)-1H-pyrazol-4-yl)-7-fluoro-4H-chromen-4-ones 6a to 6e . Structures of all novel compounds were confirmed by infrared (IR), proton nuclear magnetic resonance (¹H NMR), carbon nuclear magnetic resonance (¹³C NMR), and mass spectral data. All the synthesized compounds were screened for their antibacterial activities.     

A Hybrid Open-Framework Aluminum Phosphate-Oxalate Possessing Large Circular 12-Membered Channels

A new aluminum phosphate-oxalate, I, [N₂C₄H₁₂]Al₂(PO₄) (HPO₄)(C₂O₄)]H₂O, has been synthesized hydrothermally in the presence of structure-directing amines. The hybrid structure comprises a vertex-linkage of AlO₆ octahedra, PO₄ tetrahedra, and C₂O₄ units leading to three-dimensional connectivity. The connectivity between AlO₆ and PO₄ units are such that it forms double-six rings that are connected to each other via the oxalate units, thereby leading to the formation of a large circular 12-membered channel of width 9 Å along the c axis. The structure-directing amine along with one water molecule is situated within this channel. The connectivity also forms two different types of 8-membered channels along the a and b axes. The three-dimensional structure of I, is very similar to the naturally occurring aluminosilicate zeolite, gmelinite. Crystal data for I are: monoclinic, space group Pccm, a=9.992(1), b=11.644(1), c=12.231(1) Å, V=1423.0(2), M=438.9, Z=4, R_F=0.07.     

A new cardo bisphenol monomer containing pendant azido group and the resulting aromatic polyesters

Expanding on our strategy to synthesize aromatic step‐growth polymers containing pendant clickable azido groups via functional monomer approach, we have now designed and synthesized a new cardo bisphenol, viz., 2‐(2‐azidoethyl)‐3, 3‐bis(4‐hydroxyphenyl) isoindolin‐1‐one (PPH‐N₃). PPH‐N₃ was conveniently synthesized starting from commercially available phenolphthalein by a three‐step route in an overall yield of 65% using simple organic transformations. Aromatic (co)polyesters bearing pendant azido groups were synthesized by low‐temperature solution polycondensation of PPH‐N₃ or different molar ratios of PPH‐N₃ and bisphenol‐A (BPA) with aromatic diacid chlorides in dry dichloromethane in the presence of triethylamine (TEA) as a base. The formation of medium to reasonably high‐molecular‐weight (co)polyesters was evidenced from intrinsic viscosity and number‐average molecular‐weight measurements that were in the range 0.52–0.85 dL/g and 16,700–28,200, respectively. Tough, transparent, and flexible films could be cast from chloroform solutions of these (co)polyesters. (Co)polyesters were characterized using FTIR, ¹H NMR, ¹³C NMR spectroscopy, XRD, and TGA. The thermal curing reaction of (co)polyesters involving decomposition of azido groups was studied by DSC analysis. The chemical modification of a representative copolyester containing pendant azido groups was carried out quantitatively using catalyst‐free azide‐maleimide cycloaddition reaction with two maleimides, namely, N‐methylmaleimide and N‐hexylmaleimide. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1516–1526