π-Extended Pyrrole-Fused Heteropine: Synthesis,Properties, and Application in Organic Field-Effect Transistors

Sulfur-embedded polycyclic aromatic compounds have been used as building blocks for numerous organic semiconductors over the past few decades. While the success is based on thiophene-containing compounds, aromatic compounds that contain thiepine, a sulfur-containing seven-membered-ring arene, has been less well investigated. Here we report the synthesis and properties of π-extended pyrrole-fused heteropine compounds such as thiepine and oxepine. A π-extended pyrrole-fused thiepine exhibited a “pitched π-stacking” structure in the crystal, and exhibited a high charge carrier mobility of up to 1.0 cm² V⁻¹ s⁻¹ in single-crystal field-effect transistors.     

Persulfurated Benzene-Cored Asterisks with π-Extended ThioNaphthyl Arms: Synthesis,Structural, Photophysical and Covalent Dynamic Properties

The synthesis of regioisomeric asterisks ( 5 ) and ( 6 ) incorporating a benzene core with six 1-naphthylthio or six 2-naphthylthio arms are reported in search for new materials with optoelectronic properties. The consequences on the extension of a π system surrounding a persulfurated benzene core provide a new avenue to study the structural, photophysical, and chemical properties of such family of all-organic phosphors. It also diverts the persulfuration mechanism after two radical cyclizations for making a [5]dithiohelicene by-product ( 7 ) and favors dynamic sulfur component exchange reactions surrounding the core. These exchanges convert asterisks ( 5 ) and ( 6 ), non-phosphorescent at 20 °C to the highly phosphorescent ( 4 ) (ϕ ∼100 %, solid state at 20 °C). For asterisks ( 5 ) and ( 6 ), the absence of the typical phosphorescence of the per(phenylthio)benzene core in the solid state at 20 °C and the presence of a weak naphthalene-based phosphorescence at 77 K is attributed to an energy transfer from the triplet state of the persulfurated benzene core to the outer naphthalene moieties, resulting in an antenna system.     

Synthesis,Structures, and Properties of Highly Strained Cyclophenylene–Ethynylenes with Axial and Helical Chirality

Single and double cyclophenylene–ethynylenes (CPEs) with axial and helical chirality have been synthesized by the Sonogashira cross-coupling of di- and tetraethynyl biphenyls with a U-shaped prearomatic diiodoparaphenylene followed by reductive aromatization. X-ray crystallographic analyses and DFT calculations revealed that the CPEs possess highly twisted bent structures. Bend angles on the edge of the paraphenylene units were close to the value of [5]cycloparaphenylene (CPP)—the smallest CPP to date. The double and single CPEs possessed stable chirality despite flexible biphenyl structures because of the high strain in the diethynyl–paraphenylene moiety. In both the single and double CPEs, orbital interactions along the biphenyl axis were observed by DFT calculations in LUMO and LUMO+2 of the single CPE and LUMO+1 of the double CPE, which likely cause lowering of these orbital energies. Concerning chiroptical properties: boosting of the g_abs value was observed in the biphenyl-based double CPE, as well as the binaphthyl-based single CPE, compared to the biphenyl-based single CPE.     

Synthesis and Magnetic Properties of Polyamide Complex Containing Bithiazole Moieties

A new polyamide containing bithiazole moieties （PTA） was synthesized by the polycondensation of 2, 2＇-diamino-4, 4＇-bithiazole （DABT） and oxalyl chloride. The polymer complex was prepared from PTA and NdC13 in DMSO. They were characterized through IR and elemental analysis. The preliminary magnetic properties of the complex PTA-Nd^3＋ was investigated, it was found that the material is a ferromagnet at low temperature.     

Two New Copper(Ⅱ) Complexes with p-Cyanobenzoic Acid: Synthesis,Crystal Structures and Properties

The complexes of [Cu(bpy)(H2O)(CBA)2]n 1 and [Cu(phen)(H2O)(CBA)2]·H2O 2 based on p-cyanobenzoic acid(HCBA) have been synthesized in aqueous ethanolic solution at room temperature. The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in orthorhombic and complex 2 is of triclinic system. The results indicate the complex 1 shows a 1D chain structure bridged by two carboxylic oxygen atoms from CBA–, and complex 2 is a mononuclear structure. Through intermolecular hydrogen bonding and π...π stacking interactions, the complexes are assembled into supramolecular structures. Complex 1 has been characterized by magnetic measurements. The magnetic measurement indicates that weak ferromagnetic interaction(zJ= 0.038(5)) between the Cu2+ ions is dominant in the structure. The IR spectrum and results of thermal and elemental analyses are also presented.     

Ge−Fe Carbonyl Cluster Compounds: Ionic Liquids-Based Synthesis,Structures, and Properties

Nine Ge−Fe carbonyl cluster compounds are prepared via ionic liquids-based synthesis. This includes the novel compounds [EMIm][Fe(CO)₃I(GeI₃)], [EHIm][Fe(CO)₃I(GeI₃)], [BMIm][GeI₂{Fe(CO)₄}₂(μ-I)][AlCl₄]₂, [GeI₂{Fe(CO)₄}₂(μ-I)][Fe(AlBr₄)₃], [BMIm]₂[(FeI₂)_0.75{Fe(CO)₂I(GeI₃)₂}₂], and [EHIm][Fe(CO)₄(GeI₂)₂Fe(CO)₃GeI₃] as well as the previously reported compounds (Fe(CO)₄(GeI₃)₂, FeI₄{GeI₃Fe(CO)₃}₂, and Ge₁₂{Fe(CO)₃}₈(μ-I)₄ (EMIm: 1-ethyl-3-methylimidazolium, EHIm: 1-ethylimidazolium, BMIm: 1-butyl-3-methylimidazolium). With this series of compounds, a comparison of synthesis conditions and structural features is possible and, for instance, allows correlating the composition and structure of the respective Ge−Fe carbonyl cluster compounds with the type and acidity of the ionic liquid. With [EMIm][{GeI₃}₂Fe(CO)₃I], moreover, we can exemplarily show the thermal decomposition as a single-source precursor in the ionic liquid, resulting in bimetallic Ge−Fe nanoparticles with small size and narrow size distribution (7.0±1.4 nm).     

Correspondence on “Cyanine Dyes Containing Quinoline Moieties: History,Synthesis, Optical Properties and Applications”

In the review on “Cyanine Dyes Containing Quinoline Moieties: History, Synthesis, Optical Properties and Applications” (K. Ilina, M. Henary, Chem Eur. J. 2021 , 27, 2430; https://doi.org/10.1002/chem.202003697 ), some essential aspects were incorrectly described and discussed. To avoid further confusion, this correspondence tries to clarify both the structures and the history of some cyanine and apocyanine dyes that were not presented sufficiently.     

Synthesis and Properties of Phosphabetaine Structures: III. Phosphabetaines Derived from Tertiary Phosphines and α,β-Unsaturated Carboxylic Acids. Synthesis, Structure, and Chemical Properties

Methods of synthesis of acylate phosphabetaines by reactions of triphenylphosphine with methacrylic, cinnamic, and p-methoxycinnamic acids are developed. The phosphabetaine form is proposed to exist in equilibrium with the ⁵-oxaphospholane form. The features of methylation of the phosphabetaines are discussed.     

Synthesis,Structures, and Thermal Properties of Symmetric and Janus “Lantern Cage” Siloxanes

Symmetric and asymmetric (Janus-type) new “lantern cage” siloxanes (PhSiO_1.5)₄(Me₂SiO)₄(RSiO_1.5)₄ (R=Ph or iBu) were synthesized through reaction of all-cis-[PhSi(OSiMe₂Br)O]₄ with all-cis-[RSi(OH)O]₄ (R=Ph or iBu). These precursors were obtained by facile two or three-step reactions from commercially available compounds. The spectroscopic properties of the resulting products were fully characterized and they showed high thermal stability and sublimation without decomposition. The crystal structures clearly indicated that the internal vacancy volumes of the lantern cages are considerably larger than that of octaphenylsilsesquioxane (PhSiO_1.5)₈. DFT calculations of the lantern cage showed a distinctly different electronic state from that of octasilsesquioxane. These results suggest that lantern cage siloxanes have a characteristic “field” in the molecule.     

New π-Extended Donors: Synthesis,Characterization, Electrochemical and Electrical Conductivity Studies

A new series of tetrathiafulvalene (TTF) molecules with extended π-system was prepared by using a Wittig reaction to generate the TTF key. The process of deprotection-alkylation of thiolates provided access to a wide variety of molecules. The study of their reducing power was carried out by cyclic voltammetry. Charge transfer complexes have also been chemically prepared by using TCNQ as an electron acceptor; the electrical conductivity of their compressed powders shows insulator behavior. The IR spectra of the TCNQ salts were recorded and used to characterize and estimate the degree of charge transfer of these complexes.

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Synthesis, Properties, and Crystal and Molecular Structures of New Ni(II) Complexes with Sterically Hindered Methoxy-β-iminoketones

This paper describes a procedure for the synthesis of two new volatile complexes, C₂₂H₄₀N₂NiO₄ and C₂₀H₃₆N₂NiO₄, based on sterically hindered methoxy--iminoketones. The compounds were investigated by IR spectroscopy and DTA. Full crystal-chemical analysis has been carried out. The structures are molecular. The complexes have close geometrical characteristics; the distances are Ni–O 1.826 and Ni–N 1.842 ; the O–Ni–N chelate angle is 93.2°. The complexes have an intramolecular hydrogen bond N–H...O, estimated at 2.54 (2.08) . In both structures, the packing of complexes is similar to that in nickel(II) dipivalylmethanate.     

Two Carboxylato-bridged Binuclear Cobalt(Ⅱ) Complexes Pillared Coligands: Synthesis,Structures and Magnetic Properties

By adopting mixed-ligand strategy, two Co(Ⅱ) coordination polymers, [Co(phda)(itmb)(H_2O)_2]_n(1) and [Co(phda)(Hpytz)]_n(2)(H_2phda = 1,2-phenylenediacetate, itmb = 1-(imidazo-1-ly)-4-(1,2,4-triazol-1-yl methyl) benzene and Hpytz = 3,5-di(4-pyridyl)-1,2,4-triazolate), were hydrothermally synthesized and then characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis(TGA), powder X-ray diffraction(PXRD) and single-crystal X-ray diffraction. The single-crystal X-ray diffraction reveals that two complexes feature carboxylato-bridged binuclear subunits extended further by the nitrogen-rich coligands to form different structures. Complex 1 containing phda-bridged binuclear cobalt is developed by itmb coligand to 1D double-stranded chain, whereas complex 2 exhibits 2D open bilayers, which result from the ribbon-like carboxylate chains pillared Hpytz coligands. In addition, the magnetic susceptibilities of both compounds were measured over the temperature range of 3～300 K, and the data were analyzed well using Mag Saki software. The best fitting parameters were κ = 0.98, λ =-100 cm~(-1), ? = 588 cm~(-1) and J = 0.6 cm~(-1) for complex 1 and κ = 0.86, λ =-110 cm~(-1), ? = 756.8 cm~(-1) and J =-1.25 cm~(-1) for complex 2. The results indicate the existence of weaker ferromagnetic interaction for complex 1 and antiferromagnetic interaction for complex 2 between the metal centers in the dinuclear metal units.     

A Rare Example of Discrete Lanthanide–Lithium Tetrakis-β-Diketonates: Synthesis,Structures, and Luminescence Properties

Russian Journal of Coordination Chemistry - The reactions of functionalized lithium CF3-β-diketonate (LiL) with europium(III) and terbium(III) chlorides in acetonitrile afford heterobimetallic...     

Syntheses,Structures,and Photoluminescent Properties of Two Zn(Ⅱ) Coordination Polymers with Helical Chains Structures

Two novel coordination polymers with helical chains, {[Zn(L)(H2O)]?H2O}n(1) and {[Zn(L)(p-bix)]?3.5H2O}n(2), where H2 L = 5-(4-hydroxypyridinium-1-ylmethyl) isophthalic acid and p-bix = 1,4-bis(imidazol-1-ylmethyl)benzene, have been hydrothermally synthesized, and charac-terized by elemental analysis, powder X-ray diffraction(PXRD), IR, thermal gravimetric analyses(TGA) and also by single-crystal X-ray diffraction. Both complexes 1 and 2 crystallize inmonoclinic, space group P21/c. Compound 1 displays a two-dimensional(2D) structure with two distinct types of helical chains; 2 shows a layered coordination polymer with two types of helical chains and features an interesting 2D→3D interdigitated architecture. Meanwhile, the luminescent properties of 1 and 2 have also been investigated in detail.     

β-Diketiminato Rare-Earth Metal Complexes: The Influence of Monoatomic Substituents in the N-aryl Moieties on Structures and Properties

Treatment of β-diketiminate ligands bearing different N-aryl monoatomic substituents [HL^H = (C₆H₅)N = C(Me)CH=C(Me)NH(C₆H₅), HL^F = (2,6-F₂C₆H₃)N=C(Me)CH=C(Me)NH(2,6-F₂C₆H₃), and HL^Cl = (2,6-Cl₂C₆H₃)N=C(Me)CH=C(Me)NH(2,6-Cl₂C₆H₃)] with Ln(CH₂SiMe₃)₃(THF)₂ (Ln = Y and Lu) afforded a variety of β-diketiminato rare-earth metal complexes depending on substituents, namely, phenyl ring C–H bond activated complexes (L')(L^H)Lu(THF) ( 1b , L' = (C₆H₄)N = C(Me)CH=C(Me)N(C₆H₅)), six-coordinate homoleptic complexes (L^H)₃Ln [Ln = Y ( 1aa ), Lu ( 1bb )], five-coordinate monoalkyl complexes (L^F)₂Ln(CH₂SiMe₃) [Ln = Y ( 2a ), Lu ( 2b )], and four-coordinate dialkyl complexes (L^Cl)Ln(CH₂SiMe₃)₂ [Ln = Y ( 3a ), Lu ( 3b )]. All these complexes were characterized with NMR spectroscopy, and lutetium complexes 1b , 1bb and 3b were structurally validated by single-crystal X-ray diffraction analysis. Moreover, dialkyl complexes 3 promoted the polymerization of 2-vinylpyridine (2-VP) to produce atactic poly(2-vinylpyridine) (P2VP) with quantitative yield. On activation with an equimolar amount of [Ph₃C][B(C₆F₅)₄], complexes 3 afforded highly isotactic P2VP with an mm value up to 94 %. Both ¹H NMR spectrum and MALDI-TOF mass analysis of an oligomer indicate that the polymerization was initiated by coordination insertion of 2-VP into the Y-CH₂SiMe₃ bond.     

Fused Fluorinated Bis-β-diketones and Luminescent-Spectral Properties of Their Complexes with Europium

Russian Journal of General Chemistry - Claisen condensation of diacetylated fused aromatic and heteroaromatic compounds (fluorene, dibenzofuran, dibenzothiophene, or carbazole) with...     

Synthesis, Characterization and Crystal Structures of Lanthanide Phenoxyacetate Complexes with 1,10-Phenanthroline

IntroductionTherehasbeenconsiderableinterestinthecoordinationchemistryoflanthanidecomplexeswithcarboxylateligandsduetotheirpotentialapplicationinmolecularassembliesandluminescentprobesinsystemsofbiologicalrelevance .1 4 Ofthenumerouslanthanidecomplexesthathavebeenwidelystudied,5 9mostofthemarefoundtoexhibitavarietyofdimericorinfinitechainstructure.RecentlywehavereportedpolymericLu(POA) 3(phen)compoundinwhichlutetiumionsforminfinitechainalongtheb axisdirectionthroughthecoordinationofbridgingc…     

Synthesis,Structures, and Properties of Novel N‐Aryl‐phenanthren‐o‐iminoquinones

The interaction of 9,10‐phenanthrenquinone with primary amines has been studied. Use of sterically hindered anilines gave the phenanthren‐o‐iminoquinones in good yields. These compounds are structural analogues of o‐benzoquinones. Using single‐electron reduction, o‐iminoquinones may synthesize metal's free‐radical complexes.     

Synthesis and Properties of Poly （aryl ether ketone） Copolymers Containing 2,7-Naphthalene Moieties

IntroductionPoly(aryl ether ketone)s are high performance en-gineering plastics with outstanding physical,chemical,thermal and mechanical properties and have been ap-plied to the aerospace industry,the electronic industry,the automobile industry,the petro…     

Bromine-contained and Modified with Amino Group,D-π-A α-Cyanostilbenzene Derivative:Synthesis,Crystal Structure and Photoluminescence

A novel D-π-A type α-cyanostilbenzene derivative,(Z)-2-(4-aminophenyl)-3-(4-bromophenyl)-acrylonitrile(ABAN), was designed and synthesized, by introducing an electrondonating amino group and a heavy atom. The structure of ABAN was confirmed by FT-IR, 1H NMR, 13 C NMR spectra and single-crystal X-ray diffraction analysis. The ABAN is of orthorhombic system, space group P212121, with a = 8.6100(14), b = 9.6923(16), c = 15.705(3) ?, Mr = 299.17, V = 1310.6(4) ?3, Z = 4, Dc = 1.516 g/cm-3, μ = 3.119 mm-1, F(000) = 600, Rint = 0.038, R(I 2σ(I)) = 0.0276, w R(I 2σ(I)) = 0.0628, R(all data) = 0.0324, wR(all data) = 0.0646, completeness to theta = 25.00 was 99.8% and GOOF = 1.04. In the crystal structure, ABAN molecules were linked with each other through intermolecular C–H···π interactions and N–H···N hydrogen bonds, by which the 1D chain, 2D plane and 3D stacking structures were constructed. The photophysical properties and calculation results confirmed that ABAN possessed an intramolecular charge transfer(ICT) process. ABAN could be applied into the optoelectronic material field due to good solvent-tuned photophysical properties and highly thermal stability.