2-Methylbenz[c,d]indole and its derivatives

2-Methylbenzc,dindole was prepared from naphthostyril, 2-Methyl- and -2-methylthio-benz [c,d]indoles gave 2-[(benz[c,d]indole-2(1H)-yliden)methyl]benz[c,d]-indole in good yield. Visible spectra of methine dyes originating from this base were considered.     

Synthesis and properties of some 7H,9H-quinazolino-[3,2-b]benz[d,e]isoquinolin-7-one derivatives

A number of 7H,9H-quinazolino[3,2-b]benz[d,e]isoquinolin-7-one derivatives containing chlorine atoms, methoxy, nitro or amino groups at the 11 or 12 position of the molecule skeleton have been synthesised.The structure of the dyes obtained has been confirmed by elemental analysis, as well as by i.r. and n.m.r. spectroscopy. Electronic spectra in the visible range have also been recorded and the effect of the character of the substituents on the colour has been analysed.     

Intermediates and dyes for synthetic-polymer fibres. Benzo [b]naphtho [3,2-d]thiophene-6,7-dicarboxylic acid imides and benzimidazo dibenzothio

Benzo[b]naphtho[2,3-d]thiophene-6,7-dicarboxylic anhydride (I) is obtained y Pschorr intramolecular cyclisation of 2-(2-aminophenylthio)-1,8-naphthalic anhydride. Condensation with alkylamines and arylamines gives the corresponding imides, which colour synthetic-polymer fibres in greenish-yellow hues, and reaction with o-phenylenediamines affords the isomer mixtures of derivatives of benzimidazo[1,2-b]-dibenzothiopheno-[4,3,2-d,e] isoquinolin-10-one and of benzimidazo-[2,1-a] dibenzothiopheno-[4,3,2-d,e]isoqumolin-10-one, which dye polyester fibres bright reddish-orange. Both series of dyes have excellent fastness to light and sublimation. The colour of the dyes is discussed in relation to the isomeric compounds derived from benzo[k,1]thioxanthene-3,4-dicarboxylic anhydride (III) and from benzo[d]naphtho[1,2-b]thiophene-9,10-dicarboxylic anhydride (II). The synthesis of the individual isomers resulting from reaction of I with o-phenylenediamine is reported and their absorption maxima related to polar factors operative within each isomer.     

Spectral properties of 7H,9H-quinazolino[3,2-b]-benz[d,e]isoquinolin-7-one

The basic spectral properties (absorption and emission spectra, emission anisotropy and emission lifetime) of 7H,9H-quinazolino[3,2-b]benz[d,e]isoquinolin-7-one were measured and compared with theoretical predictions.On the basis of Perrin's and Kawski's theories the rotatory motion of the dye was also studied. The electric dipole moments in both ground and excited states and the orientation of the transition moments were obtained.     

Molecular relaxation processes in poly(N-acryloyl-10,11-dihydrodibenz [b, f]azepine)

The preparation and homopolymerization of N-acryloyl-10,11-dihydrodibenz[b, f]azepine is described. The relaxation behaviour is characterized using dielectric relaxation, pulsed n.m.r. and thermally stimulated depolarization (t.s.d.) techniques. In order to assist the assignment of relaxation data to molecular behaviour 5-chloroacetyl and 5-propionyl derivatives of iminobibenzyl were prepared and studied by dielectric relaxation in the matrix-isolated state. Comparison with N-ethyl carbazole under similar conditions revealed the existence of a relaxation in the polymer associated with nitrogen inversion in addition to a relaxation due to the glass transition. The data may be useful in studies relating to the pharmacological activity of the dibenz[b, f]azepine ring system.     

Synthesis and photophysical properties of structural isomers of novel 2,10-disubstituted benzofuro[2,3-e]naphthoxazole-type fluorescent dyes

Structural isomers of novel 2,10-disubstituted benzofuro[2,3-e]naphthoxazole fluorescent dyes have been synthesized. The phtophysical properties have been investigated in solution and in the solid state. The absorption and fluorescence intensities of the naphth[1,2-d]oxazoles are much stronger than those of the naphth[2,1-d]oxazoles in solution. Moreover, in the solid state, the emission intensities of the former are typically much stronger than those of latter isomers. To understand the differences in photophysical properties, semi-empirical molecular orbital calculations and the X-ray crystallographic analyses have been performed.     

Absorption properties of an inverted cucurbit[7]uril-based porous coordination polymer induced by [ZnCl4]2 − anions

Coordination of an inverted cucurbit[7]uril (iQ[7]) with a series of alkali cations (A⁺), revealed that iQ[7] can interact with potassium to form iQ[7]-K⁺-based porous coordination polymer in the presence of [ZnCl₄]^2 − anions as a structure directing agent. Unexpectedly, isothermal titration calorimetry revealed no obvious interaction of iQ[7] with any A⁺ cation. Moreover, the iQ[7]-K⁺-based porous coordination polymer showed selective sorption of polar volatile organics, which may have potential applications for molecular sieves, sensors, and absorption and separation processes.     

Optically active poly[thio-1-(N,N-diethylaminomethyl) ethylene]

Poly[thio-1-(N,N-diethylaminomethyl) ethylene] [poly(TDAE)] of different optical purities were prepared by stereoelective polymerization of racemic N,N-diethyl-N-(thiirane-2-ylmethyl) amine (TDAE) using a (1:1) $\text{ZnEt}{}_2\text{R}$ (?) 3,3-dimethyl 1,2-butanediol (R(?)DMBD) chiral initiator system. Optically enriched TDAE samples were isolated as residual monomers. These monomers were thermally polymerized to give optically active poly(TDAE) with randomly distributed R and S repeat units in various proportions. The configuration of the enantiomer preferentially incorporated into growing chains during the stereoelective polymerization was determined as R on the basis of the presence of a positive Cotton effect at 260 nm in the c.d. spectrum of residual monomers. This configuration agrees well with the known homosteric character of the $\text{ZnEt}{}_2\text{(?)}\text{DMBD}$ initiator system. ¹³C n.m.r. spectra of the different optically active poly(TDAE) samples and those of more or less stereoregular racemic ones were compared. It was found that the carbon atom of the main chain methine group is the only one which is stereosensitive. Observed triad effects were used to determine the degree of isotacticity of optically active poly(TDAE)s prepared by thermal polymerization of partly enriched monomers. The stereoelectivity of the initiator system and the optical activity of optically pure TDAE and poly(TDAE) were deduced. Side-chain nitrogen atoms did not show any competitive effect with sulphur atoms in the coordination process to the chiral initiator system.     

CONDENSATION PRODUCTS OF 7H-BENZO[DE]NAPHTHACENE-7-ONE

Condensation reaction of 7H-benzo[de]naphthacene-7-one (1 Kohno, Y., Kohno, M., Saito, Y. and Inokuchi, H. 1975. Crystal Structure of Tetrabenzo[a,cd,j,lm]perylene. Acta Cryst., B31: 2076–2080.  [Google Scholar]) was conducted in fused salt using zinc dust at 275°C for 2 h. The reaction products were isolated by column chromatography and then purified by recrystallization, yielding crystals of orange-yellow needles as the main product. This compound with an absorption maximum at 450 nm was identified as trinaphtho[2,3-c; 2′,1′,8′-fgh; 2″,1″,8″-uva]-pentaphene by one-dimensional and two-dimensional ¹H NMR spectroscopy, which was one of expected condensation products. We are now trying to isolate the other expected condensation products, benzo[vwx]dinaphtho[2,1-a; 8′,1′,2′-cde]hexaphene and benzo[cd]naphtho[2,3-f]anthra[3,2,1-lm]perylene, from the byproducts.     

Computing the Szeged and PI Indices of VC5C7[p,q] and HC5C7[p,q] Nanotubes

In this paper we give a GAP program for computing the Szeged and the PI indices of any graph. Also we compute the Szeged and PI indices of VC₅C₇ [ p,q] and HC₅C₇ [ p,q] nanotubes by this program.     

Chinoxaline. XXVI. Synthese von bis-azolo[a,c]kondensierten Chinoxalinen. I. Darstellung aus 4-substituierten 1,2,3-Triazolo[1,5-a]chinoxalinen

Quinoxalines. XXVI. Synthesis of Bis-azolo[a,c]-fused Quinoxalines. I. Synthesis from 4-Substituted 1,2,3-Triazolo[1,5-a]quinoxalines The synthesis of bis-azolo-fused quinoxalines of type. 6 is described. The new bisazolo-fused compounds 9, 10a, b, 12 , and 16 were synthesized from the 4-substituted 1,2,3-triazolo-[1,5-a]quinoxalines 7, 8, 11 , and 13 by intramolecular cyclization reactions. The structures were determined by microanalysis, i.r., ¹H-n.m.r., and mass spectra.     

Hexachloroplatinate(IV) anion-induced cucurbit[5]uril and cucurbit[8]uril supramolecular assemblies with linear channels

Two Q[n]-based porous compounds, Q[5]·[PtCl₆]^2 −·2H₃O·12H₂O and 2Q[8]·[PtCl₆]^2 −·2H₃O·74H₂O in cooperating the hexachloroplatinate(IV) anion ([PtCl₆]^2 −) as an inorganic structure directing agent are demonstrated. The driving forces for the formation of such novel Q[n]-based porous compounds are considered to be the outer surface interactions of Q[n]s, including dipole interactions between Q[n]s and ion-dipole interactions between [PtCl₆]^2 − anions and Q[n]s. Moreover, the Q[5]-based porous compound displays absorption distinctness for tetrachloromethane, whereas the Q[8]-based porous compound displays absorption distinctness for methanol.     

The synthesis and photochromism of a 2,2-diaryl-6-styryl-2H-[1]benzopyran: Unexpected palladium-mediated ring-contraction of a 6-bromo-2,2-diaryl-2H-[1]benzopyran

The ligand-free Pd-mediated reaction between styrene and a 6-bromo-2,2-diaryl-2H-[1]benzopyran proceeded anomalously to give a 2-(diarylmethyl)-5-styrylbenzofuran via a tandem Heck coupling - ring-contraction process; none of the styryl substituted 2,2-diaryl-2H-[1]benzopyran was observed. A 2,2-diaryl-6-styryl-2H-[1]benzopyran resulted from the condensation between 4-hydroxystilbene and a 1,1-diarylpropynol and which exhibited photochromism through the reversible electrocyclisation of the pyran unit; no isomerisation - electrocyclisation of the stilbene moiety was detected.     

Synthesis of 7H-Benzo [de] -s-triazolo [5,1-a] isoquinolin-7-one derivatives and study of their fluorescent properties

N-Aminonaphthalimide (4a) and N-amino-5-nitronaphthalimide (4b) prepared from acenaphthene (1a) and 5-nitroacenaphthene (1b) by oxidation, cyclization with acetic anhydride and subsequent treatment with hydrazine sulphate were reacted with a variety ofcarboxylic acid amides such as formamide, acetamide, benzamide, cinnamic amide, coumarin-3-carboxamide and urea using zinc chloride in ethanediol at 150°C to give the 10-substituted and 6-nitro-10-substituted-7H-benzo[de]-s-triazolo[5,1-a]-isoquinolin-7-ones (6a–6f and 6b–6m), respectively. Acetylation of the 10-amino derivative 6f and reductive acetylation of the 6-nitro-10-substituted derivatives 6h–6m gave the 10-acetamido, 6-acetamido-, 6-acetamido-10-methyl, 6-acetamido-10-phenyl, 6-acetamido-10-(2-styryl), 6-acetamido-10-(coumarin-3-yl) and 6,10-bisacetamido derivatives (6g, 7a–7f), respectively. The fluorescent properties of the compounds 6a–6e and 7a–7f were studied. Compounds 6a, 6b and 7e were applied as fluorescent whiteners on polyester fibres and gave satisfactory results.     

Synthesis of highly fluorescent coumarinyl chalcones derived from 8-acetyl-1,4-diethyl-1,2,3,4-tetrahydro-7H-pyrano[2,3-g]quinoxalin-7-one and their spectral characteristics

A series of novel coumarin based chalcones were synthesized by the classical crossed aldol condensation reaction of 8-acetyl-1,4-diethyl-1,2,3,4-tetrahydro-7H-pyrano[2,3-g]quinoxalin-7-one and various substituted benzaldehydes. These novel ketocoumarin derivatives having a 1,4-diethyl-1,2,3,4-tetrahydroquinoxaline framework exhibited brilliant fluorescence. The novel chalcones absorbed in the range of 458-523 nm in various solvents. The wavelength of maximum absorption of these chalcones was found to be significantly longer than their simple acyl derivative known in the literature. The dyes displayed longer wavelength of absorption in the high polarity solvents compared to non-polar solvents. Thermogravimetric analysis of the chalcones revealed that the chalcones possess good thermal stability.     

Blue organic light-emitting diodes using novel spiro[fluorene-benzofluorene]-type host materials

Deep blue colored, fluorescent, spiro-type host materials, 5-[4-(1-naphthyl)phenyl]-spiro[fluorene-7,9′-benzofluorene] and 5,9-bis[4-(1-naphthyl)phenyl]-spiro[fluorene-7,9′-benzofluorene] were designed and successfully prepared by the Suzuki reaction. The electroluminescence characteristics of the two compounds as blue host materials doped with blue dopant materials, diphenyl[4-(2-[1,1;4,1]terphenyl-4-yl-vinyl)phenyl]amine and 1,6-bis[(p-trimethylsilylphenyl)amino]pyrene (SPP) were evaluated. The device used comprised ITO/N,N′-bis-[4-(di-m-tolylamino)phenyl]-N,N′-diphenylbiphenyl-4,4′-diamine)/bis[N-(1-naphthyl)-N-phenyl]benzidine/Host:5% dopant/tris(8-hydroxyquinolinato)aluminium/Al–LiF. The device obtained from 5-[4-(1-naphthyl)phenyl]-spiro[fluorene-7,9′-benzofluorene] doped with 1,6-bis[(p-trimethylsilylphenyl)amino]pyrene displayed high color purity (0.138, 0.138) and high efficiency (3.70 cd/A at 7 V).     

A molecular simulation study of cavity size distributions and diffusion in para and meta isomers

Polysulfone based on bisphenol A has been extensively used as a material for membrane-based gas separation. For polymers with aromatic rings in their backbones, such as polysulfones and polyimides, changing the connecting bond positions from meta to para seems to increase their permeability and diffusivity to gases. Cavity size distributions of three isomer pairs (PSF and 3,4′-PSF, PSF-P and PSF-M, 6FDA-6FpDA and 6FDA-6FmDA) are calculated through molecular simulation. The diffusivity of small molecules in these isomers is also obtained by molecular dynamics. For all three isomer pairs, the average cavity size in para isomers is larger than in meta isomers. The molecular dynamics determined diffusion coefficients of neon in para isomers are also larger than in meta isomers. These results are consistent with the experimental observation that room-temperature gas diffusion in para isomers is faster than in meta isomers.     

Theoretical studies of the electronic structures and optical properties of stable blue-emitting polymer based on 4H-cyclopenta-[def]-phenanthrene

Geometries, ionization potentials (IPs), electron affinities (EAs) and optical properties of two series of π-conjugated oligomers (2,6-(4,4-bis(2-ethylthexyl)-4H-cyclopenta-[def]-phenanthrene))_nCPPn (2,6-(4,4-bis(2-ethylthexyl)-8,9-dihydro-4H-cyclopenta-[def]-phenanthrene))_nHCPPn (n = 1-4) were studied theoretically. The ground and the excited state geometries were optimized by B3LYP and CIS methods with 6-31G^∗ basis sets, respectively. The absorption and the emission spectra were calculated by TD-B3LYP method. The lowest-lying absorption is assigned to π → π^∗ transition, and the fluorescence can be described as originating from the ¹[ππ^∗] excited state. IPs, EAs, H-L gaps, absorption and emission properties of PCPP (n = ∞) and PHCPP (n = ∞) were obtained by extrapolation method. The fact that the lowest-lying absorption and the emission of PCPP are blue-shifted compared with those of PHCPP, can be interpreted by the smaller effective repeating units of PCPP. The extra absorption band at 289 nm of PCPP is contributed by the π → π^∗ transition involving the extra π-conjugation CC bond.