Search results for "Substituent"
showing 10 items of 353 documents
Preparation and Structure of Diexo-Oxanorbornane-fused 1,3-Heterocycles
2004
Via the reaction of diexo-oxanorbornanedicarboxylic anhydride with toluene, the diexo-aroylcarboxylic acid (3a) was prepared, which exists partly as the tautomeric lactol (3b). With bifunctional reagents, 3a yields fused heterocycles containing three-six rings. Thus, alkylenediamines result in imidazole- and 1,3-diazepine-fused oxygen- bridged isoindolones (6a,b), alkanolamines form the oxazole- and 1,3-oxazine-fused oxanorbornene derivatives (7a-c), and o-phenylenediamine undergoes cyclization to furnish the condensed benzimidazole (8). The reaction of 3a with diexo- aminonorbornanecarbohydrazide yields a pyrimidopyridazine containing six condensed rings (9). In a similar reaction with die…
The Chemistry of [1,2,3]Triazolo[1,5- a] pyridines
2003
The reactivity of [1,2,3]triazolo[1,5-a]pyridines 1 is described. Triazolopyridines react with electrophiles in two contrasting ways, giving 3-substituted triazolopyridines 2, or products 3, resulting from triazolo ring opening with loss of molecular nitrogen. The triazolopyridines can be lithiated at -40 degrees C by lithium diisopropylamide in ether giving regiospecifically the 7-lithio derivative. Bromotriazolopyridines have activation towards nucleophilic substitution at position 5 and 7, and benzenoid inertness at position 6. The parent compound 1a is easily hydrogenated giving tetrahydrotriazolopyridine 11a in high yield; when the triazolopyridines have substituents, the hydrogenation…
Conformational investigation of α,β-dehydropeptides. XVI. β-turn tendency in Ac-Pro-ΔXaa-NHMe: crystallographic and theoretical studies
2006
The crystal structures of two diastereomeric alpha,beta-dehydrobutyrine peptides Ac-Pro-(Z)-DeltaAbu-NHMe (I) and Ac-Pro-(E)-DeltaAbu-NHMe (II) have been determined. Both dehydropeptides adopt betaI-turn conformation characterized by the pairs of (phi(i+1), psi(i+1)) and (phi(i+2), psi(i+2)) angles as -66, -19, -97, 11 degrees for I and -59, -27, -119, 29 degrees for II. In each peptide, the betaI turn is stabilized by (i + 3) --> i intramolecular hydrogen bonds with N...O distance of 3.12 A for I and 2.93 A for II. These structures have been compared to the crystal structures of homologous peptides Ac-Pro-DeltaVal-NHMe and Ac-Pro-DeltaAla-NHMe. Theoretical analyses by DFT/B3LYP/6-31 + G** …
Imparting hysteretic behavior to spin transition in neutral mononuclear complexes
2016
A series of spin transition neutral compounds [FeL(NCS)2] has been synthesized and characterized by means of magnetic susceptibility studies, X-ray diffraction, IR and Mossbauer spectroscopic, and calorimetric measurements (L = N,N-bis((3-alkoxypyridin-2-yl)methylene)-propane-1,3-diamine, number of carbon atoms in chains (n) = 4, 12, 14, 16, 18, 20). The shortest chain compound is crystalline and displays a gradual spin transition above ambient temperature. Growing the aliphatic substituent up to n = 12 and 14 leads to loss of crystalline order and deterioration of magnetic properties. At the critical chain length n = 16 and above, the compounds undergo a phase transition reflected by a spi…
Carborane-stilbene dyads: influence of substituents and cluster isomers on the photoluminescence properties
2017
Two novel styrene-containing meta-carborane derivatives substituted at the second carbon cluster atom (Cc) with either a methyl (Me), or a phenyl (Ph) group, are introduced herein alongside with a new set of stilbene-containing ortho- (o-) and meta- (m-) carborane dyads. The latter set of compounds has been prepared from styrenecontaining carborane derivatives via Heck coupling reaction. High regioselectivity has been achieved for these compounds by using a combination of palladium complexes [Pd2(dba)3]/[Pd(t-Bu3P)2] as a catalytic system, yielding exclusively E isomers. All compounds have been fully characterized and the crystal structures of seven of them analyzed by X-ray diffraction. Th…
Fine‐Tuning of Photophysical and Electronic Properties of Materials for Photonic Devices Through Remote Functionalization
2012
We report four new iridium(III) complexes of the type [Ir(ppy)2(N?N)][PF6] in which N?N is a 4,6-diphenyl-2,2`-bipyridine and the 4-phenyl ring is substituted at either the para or meta positions [4-Me, N?N = 1; 4-Br, N?N = 2; 3,5-Br2, N?N = 3; 3,5-(C6H4-4-NPh2)2, N?N = 4]. The complexes have been fully characterized, and single-crystal diffraction analyses of [Ir(ppy)2(N?N)][PF6] (N?N = 13) confirmed that each [Ir(ppy)2(N?N)]+ cation exhibits face-to-face p-stacking between the pendant phenyl substituent of the N?N ligand and the cyclometallated phenyl ring of an adjacent [ppy] ligand. In solution, the complexes are short-lived emitters; the emission maxima for [Ir(ppy)2(1)][PF6], [Ir(ppy)…
Efficient Green Light-Emitting Electrochemical Cells Based on Ionic Iridium Complexes with Sulfone-Containing Cyclometalating Ligands
2013
A new approach to obtain green-emitting iridiumA complexes is described. The synthetic approach consists of introducing a methylsulfone electron-withdrawing substituent into a 4-phenylpyrazole cyclometalating ligand in order to stabilize the highest- occupied molecular orbital (HOMO). Six new complexes have been synthe- sized incorporating the conjugate base of 1-(4-(methylsulfonyl)phenyl)-1 H- pyrazole as the cyclometalating ligand. The complexes show green emission and very high photoluminescence quantum yields in both diluted and concentrated films. When used as the main active component in light-emit- ting electrochemical cells (LECs), green electroluminance is observed. High efficienci…
Copolymerization of ethene with styrene using different methylalumoxane activated half-sandwich complexes
1997
Ethene was copolymerized with styrene using five different methylalumoxane (MAO) activated half-sandwich complexes of the general formula Me 2 Si(Cp)(N-R)MCl 2 , varying the substituents on the cyclopentadienyl ring and the substituent on the amide (Cp = tetramethylcyclopentadiene CBT, 1-indenyl IBT, 3-trimethylsilyl-1-indenyl SIBT, or fluorenyl FBZ, R = tert-butyl (complexes CBT,IBT, SIBT, FBZ ) or benzyl CAT), as well as the metal center ( M = Ti, except FBZ: M = Zr). Polymerization behavior was analyzed with respect to catalyst activity and polymerization kinetics, styrene incorporation, copolymer microstructure, and molecular weight. All complexes produced random poly(ethene-co-styrene)…
Effect of the Substituent Position on the Anionic Copolymerization of Styrene Derivatives: Experimental Results and Density Functional Theory Calcula…
2019
In a combined synthetic, kinetic and theoretical study, the living anionic copolymerization of styrene and its ring-methylated derivatives ortho-, meta-, and para-methylstyrene (MS) was examined by real-time 1H NMR spectroscopy in the nonpolar solvents toluene-d8 and cyclohexane-d12 as well as by density functional theory calculations. Based on the NMR kinetics data, reactivity ratios for each comonomer pair were determined by the Kelen–Tudős method and numerical integration of the copolymerization equation (Contour software). The reaction pathway was modeled and followed by density functional theory (DFT) calculations to validate and predict the experimentally derived reactivity ratios. Un…
Substituent effects on the photophysical properties of fluorescent 2-benzoylmethylenequinoline difluoroboranes: A combined experimental and quantum c…
2013
Abstract In this study, we demonstrate a successful synergy between theory and experiment and report on the photophysical properties of a recently synthesized series of substituted 2-benzoylmethylenequinoline difluoroboranes with a view towards the effect of substitution on their properties. In general difluoroboranes are known to have a bright fluorescence but for some analogs the properties are not fully understood. Quantum chemistry methods have been applied in order to explain a complex structure of the absorption and emission spectra and to gain an insight into the charge redistribution upon the excitation of the investigated molecules. We demonstrate that the spectra of this important…