<Emphasis Type="Italic">Tetra</Emphasis>-EDOT substituted 3D electrochromic polymers with lower band gaps

A couple of novel electrochromic materials poly(2,3,4,5-tetrakis(2,3-hydrothieno[3,4-b]dixin-5-yl)-1-methyl-1H-pyrrole) (P(t-EDOT-mPy)) and poly(5,5′,5′′,5′′′-(thiophene-2,3,4,5-tetrayl)tetrakis(2,3-dihydrothieno[3,4-b][1,4]dioxine)) (P(t-EDOT-Th)) are electrodeposited via multi-position polymerization of their tetra-EDOT substituted monomers t-EDOT-mPy and t-EDOT-Th, respectively. Compared with the linear 2D structured poly(thiophene) (E _g=2.2 eV) and poly(2,5-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)thiophene) (E _g=1.7 eV), P(t-EDOT-Th) (E _g=1.62 eV) has the lowest band gap. Hence, we speculate that the band gaps of the two polymers, having 3D structures, are decreased in contrast to non-substituted polymers or bi-EDOT substituted polymers, thiophene and 1-methyl-1H-pyrrole. The results indicated that P(t-EDOT-Th) thin films are more stable and show higher transmittance amid two polymers, which may find their utilization in organic optoelectronics.     

Nenitzescu synthesis of carbamate indole derivatives from <Emphasis Type="Italic">N,N′</Emphasis>-bis(methoxycarbonyl)-<Emphasis Type="Italic">p</Emphasis>-benzoquinone diimine

N,N′-Bis(methoxycarbonyl)-p-benzoquinone diimine reacted with 4-(cyclohex-1-en-1-yl)-and 4-(cyclopent-1-en-1-yl)morpholines in methylene chloride at room temperature to give morpholino-substituted cyclohexane-and cyclopentane-fused indole derivatives. Heating of the latter in boiling 10% hydrochloric acid led to the formation of methyl 6-(methoxycarbonylamino)-1,2,3,4,4a,9a-hexahydro-9H-carbazole-9-carboxylate and methyl 7-(methoxycarbonylamino)-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole-4-carboxylate, respectively. The reaction of N,N′-bis(methoxycarbonyl)-p-benzoquinone diimine with 4-benzylaminopent-3-en-2-one in CH₂Cl₂ in the presence of BF₃·Et₂O on heating gave methyl 3-acetyl-2-methyl-(5-methoxy-carbonylamino)-1H-indole-1-carboxylate.     

Quantum-chemical study of lutetium,ytterbium, and gadolinium phthalocyaninates PcLnCl

Structural parameters and IR spectra of the (¹A₁//C_4v)-PcLuCl, (²B₂//C_4v)-PcYbCl, and (⁸A₂//C_4v)-PcGdCl molecules, (²A₂//C_4v)-Pc⁺LuCl, (3B₁//C_4v)-Pc⁺YbCl, and (⁹A₁//C_4v)-Pc⁺GdCl cations, (¹A_g//D_2h)-PcLuCl₂LuPc dimer, and PcLuCl···PcLuCl coaxial molecular pair have been simulated using the DFT (U) PBE0/SDD method. The PcLnCl (Ln = Lu, Yb, Gd) molecules have exhibited the equilibrium Ln–N bond length of 222, 223, and 230 pm, the Ln–Cl bond length of 245, 246, and 253 pm, the dipole moment of 4.73, 4.57, and 4.84 D directed from Cl to Ln, and ionization potential of 6.6 eV. β-Decay (¹A₁//C_4v)-Pc¹⁷⁷LuCl → (¹A₁//C_4v)-(Pc^177mHfCl)⁺ occurs with no significant change of the charge on the metal atom.     

Derivatives of α,β-dehydroamino acids: V. Intramolecular cyclization of 2-{2-[(<Emphasis Type="Italic">Z</Emphasis>)-1-Benzamido-2-phenylvinyl]acetamidomethyl}benzimidazole

Reaction of 4-benzylidene-2-phenyl-1,3-oxazol-5(4H)-one with 2-(1H-benzimidazol-2-yl)ethaneamine led to the formation of 2-{2-[(Z)-1-benzamido-2-phenylvinyl]acetamidomethyl}benzimidazole that in a reaction with hexamethyldisilazane in DMF gave 5-benzylidene-1-(1H-benzimidazol-2-yl)-2-phenyl-3,5-dihydro-4H-imidazol-4-one. In the presence of K₂CO₃ in dioxane the reaction with hexamethyldisilazane resulted in the product of intramolecular addition, N-(4-benzyl-3-oxo-1,2,3,4-tetrahydropyrazino[1,2-a]-benzimidazol-4-yl)benzamide     

The scaling behavior of the second virial coefficient of linear and ring polymer

The scaling behavior of the second virial coefficient of ring polymers at the theta temperature of the corresponding linear polymer(θ_L) is investigated by off-lattice Monte Carlo simulations. The effects of the solvents are modeled by pairwise interaction between polymer monomers in this approach. Using the umbrella sampling, we calculate the effective potential U(r) between two ring polymers as well as the second virial coefficient A_2 of ring polymers at θ_L, which results from a combination of 3-body interactions and topological constraints. The trend in the strength of the effective potential with respect to chain length shows a non-monotonic behavior, differently from that caused only by topological constraints. Our simulation suggests that there are three regimes about the scaling behavior of A_2 of ring polymers at θ_L: 3-body interactions dominating regime, the crossover regime, and the topological constraints dominating regime.     

Catalytic alkylation of cycloalkaneindoles and tetrahydro-γ-carboline with 9-oxiranylmethylcarbazole

Catalytic alkylation of substituted indoles such as cycloalkaneindoles and tetrahydro-γ-carboline using 9-oxiranylmethylcarbazole leads to the formation of 1-(carbazol-9-yl)-3-{dihydrocycloalkane[b]indol-4(1H)-yl}propan-2-ols and 1-(carbazol-9-yl)-3-{2,8-dimethyl-3,4-dihydro-1H-pyrido[4,3-b]indol-5(2H)-yl}propan-2-ol, conjugates containing 2-hydroxypropylene spacer.     

Synthesis of 5,8-Diamino-Substituted Pyrano[4″,3″:4′,5′]pyrido[3′,2′:4,5]thieno[3,2-<Emphasis Type="Italic">d</Emphasis>]pyrimidines and Pyrimido[4′,5′:4,5]thieno[2,3-<Emphasis Type="Italic">c</Emphasis>]isoquinolines

Ethyl 1-amino-8,8-dimethyl-5-(piperidin-1-yl)-8,9-dihydro-6H-pyrano[4,3-d]thieno[2,3-b]pyridine-2-carboxylate and ethyl 1-amino-5-(piperidin-1-yl)-6,7,8,9-tetrahydrothieno[2,3-c]isoquinoline-2-carboxylate reacted with benzoyl isothiocyanate to give the corresponding 1-thioureido derivatives which underwent cyclization to 2,2-dimethyl-5-(piperidin-1-yl)-10-thioxo-1,4,10,11-tetrahydro-2H-pyrano[4″,3″:4′,5′]pyrido-[3′,2′:4,5]thieno[3,2-d]pyrimidin-8(9H)-one and 5-(piperidin-1-yl)-10-thioxo-1,2,3,4,10,11-hexahydropyrimido-[4′,5′:4,5]thieno[2,3-c]isoquinolin-8(9H)-one. The cyclization products were converted into 8-chloro derivatives, and the chlorine atom therein was replaced by various amines.     

Nickel(II) complexes prepared from NNN type ligands and pseudohalogens

Six nickel(II) complexes, using azide and thiocyanate ions, have been synthesized from bis-2,6(pyrazol-1-yl)pyridine (pp) and some methyl derivatives, 2-(3,5-dimethyl(pyrazol-1-yl)-6-(pyrazol-1-yl)pyridine (app) and bis-2,6(3,5-dimethyl(pyrazol-1-yl) pyridine (dmpp) in non-aqueous media. The complex structures were analyzed using elemental analysis, IR spectroscopy and thermogravimetry. Appropriate crystals of complex, containing azide [Nipp(N₃)₂]·MeOH (I) and thiocyanate [Nidmpp(SCN)₂·MeOH] (VI) were prepared and the molecular structures determined using X-ray diffraction. Complex I was seen to be dinuclear as stated in literature, space group P2₁/n, monoclinic, a=10.503, b=10.681, c=13.291 Å, β=106.56° and Z=2 whereas complex VI was found to be mononuclear, space group P2₁/n, monoclinic, a=8.646, b=12.614, c=20.697 Å, β=97.18° and Z=2. The Ni(II) coordination in both complexes were octahedral. Thermogravimetric studies showed azide containing structures to resemble the characteristics of explosive materials. Coordinative MeOH were seen to leave the structure in thiocyanate containing complexes, followed by irregular degradation above 300°C.     

New Quinoxaline-Containing Monomers for Narrow-Bandgap Polymers

Two new fused quinoxaline-containing monomers—2,3-bis(9-(2-decyltetradecyl)-9H-carbazol-3-yl)dithieno[3,2-f:2'3'-h]quinoxaline (М1) and 2,5-di(nonadecan-3-yl)bis[1,3]thiazolo[4,5-a:5',4'-c]bisthieno[3,2-h:2',3'-j]phenazine (М2)—have been synthesized in high yields of 88 and 83% as promising building blocks of D-A polymers for photovoltaic applications. The optical bandgaps, found from the absorption edge, are 2.79 and 2.88 eV, respectively. The HOMO/LUMO energies of М1 and М2 are–5.83/–2.96 and–5.83/–2.98 eV, respectively. Both monomers have low-lying HOMO levels, which is favorable for a high open-circuit voltage and a high stability in air in the development of PSCs. The E _g ^ec values of monomers М1 and М2 are 2.87 and 2.85 eV and are consistent well with the optical bandgap (2.79 and 2.88 eV, respectively).     

Slight Structural Disorder in Bithiophene-based Random Terpolymers with Improved Power Conversion Efficiency for Polymer Solar Cells

A series of random terpolymers P2-P5 were designed and synthesized by randomly embedding 5 mol%, 10 mol%, 15 mol%and 25 mol% feed ratios of low cost 2,2-bithiophene as the third monomer to the famous donor-acceptor(D-A) type copolymer PTB7-Th(P1). All polymers showed similar molecular weight with number-average molecular weight(Mn) and weight-average molecular weight(Mw) in the range of(59-74) and(93-114) kg·mol~(-1), respectively, to ensure a fair comparison on the structure-property relationships.Compared with the control copolymer PTB7-Th, the random terpolymers exhibited enhanced absorption intensity in a wide range from400 nm to 650 nm in both solution and film as well as in polymer/PC71 BM blends. From grazing incident wide-angle X-ray diffraction(GIWAXS), compared with the regularly alternated copolymer PTB7-Th, the random terpolymers demonstrated mild structural disorder with reduced(100) lamellar stacking and slightly weakened(010) π-π stacking for the polymers as well as slightly reduced PC71 BM aggregation in polymer/PC71 BM blends. However, the measured hole mobility for terpolymers((1.20-3.73) × 104-cm2·V-1·s~(-1)) was evaluated to be comparable or even higher than 1.35 × 10~(-4) cm~2·V~(-1)·s-1 of the alternative copolymer. Enhanced average power conversion efficiency(PCE) from 7.35% to 8.11% and 7.79% to 8.37% was observed in both conventional and inverted device architectures from copolymer P1 to terpolymers P4, while further increasing the 2,2-bithiophene feed ratio decreased the PCE.     

Synthesis of Dicarboxylic Acid Amides and Diamides on the Basis of [4-(4-Methoxyphenyl)tetrahydro-2<Emphasis Type="Italic">H</Emphasis>-pyran-4-yl]methanamine

The condensation of various nonaromatic amines with ethyl N-{[4-(4-methoxyphenyl)tetrahydro-2H-pyran-4-yl]methyl}oxamate prepared from [4-(4-methoxyphenyl)tetrahydro-2H-pyran-4-yl]methanamine and diethyl oxalate afforded the corresponding N,N'-disubstituted oxamides. N-Aryloxamides were synthesized by the reaction of [4-(4-methoxyphenyl)tetrahydro-2H-pyran-4-yl]methanamine with ethyl N-aryloxamates. The condensation of N-{[4-(4-methoxyphenyl)tetrahydro-2H-pyran-4-yl]methyl}succinamic acid with primary amines gave N,N'-disubstituted siccinamides.     

Low-melting salts with the [Cr<Superscript>III</Superscript>(NCS)<Subscript>4</Subscript>(1,10-phenanthroline)]<Superscript>−</Superscript> complex anion: Syntheses,properties, and structures

Four new low melting salts, “Ionic Liquids” consisting of the [Cr^III(NCS)₄(Phen)]^? complex monoanion and imidazolium based cations A, with A = 1-ethyl-3-methylimidazolium (EMIm), 1-butyl-3-methylimidazolium (BMIm), 1,3-dimethyl-2,4,5-triphenylimidazolium (DML), and 1,2,3,4,5-pentamethyl-imidazolium (PMIm), were investigated. Single-crystal X-ray investigations established the structures of the four compounds. (EMIm)[Cr(NCS)₄(Phen)] (I): triclinic, \(P\bar 1\), a = 8.1382(6), b = 10.4760(8), c = 16.003(1) Å, α = 90.330(4)°, β = 94.759(4)°, γ = 107.305(4)°, Z = 2, R ₁(F)/wR ₂(F ²) = 0.0650/0.1770; (BMIm)[Cr(NCS)₄(Phen)] (II): triclinic, \(P\bar 1\), a = 8.5545(4), b = 9.8620(4), c = 16.6762(6) Å, α = 92.503(2)°, β = 97.517(2)°, γ = 91.249(2)°, Z = 2, R ₁(F)/wR ₂(F ²) = 0.0393/0.0848; (DML)[Cr(NCS)₄(Phen)] · C₃H₆O (III): triclinic, \(P\bar 1\), a = 11.0475(9), b = 13.589(1), c = 14.582(1) Å, α = 83.013(4)°, β = 87.116(4)°, γ = 70.333(5)°, Z = 2, R ₁(F)/wR ₂(F ²) = 0.0407/0.1023; (PMIm)[Cr(NCS)₄(Phen)] · C₃H₆O (IV): orthorhombic, Pbca, a = 17.379(1), b = 16.514(1), c = 22.304(1) Å, Z = 8, R ₁(F)/wR ₂(F ²) = 0.0460/0.1107 (in addition III and IV contain co-crystallized acetone molecules). Each compound was characterized by elemental analysis, NMR, IR, und UV-Vis spectroscopy. Magnetic properties were derived from NMR investigations (EVANS method). All four compounds are paramagnetic with effective magnetic moments of spin-only Cr^III. Melting points were obtained from DSC measurements. All melting points are higher than required for “Ionic Liquids”, but nevertheless “low” for molten salts.     

Cyclization of trifluoro-<Emphasis Type="Italic">N</Emphasis>-(prop-2-yn-1-yl)methanesulfonamides to <Emphasis Type="Italic">N</Emphasis>-(hydroxymethyl)-1,2,3-triazoles

Three-component heterocyclizations of trifluoro-N-(prop-2-yn-1-yl)methanesulfonamide, trifluoro-N-pheny-N-(prop-2-yn-1-yl)methanesulfonamide, and trifluoro-N,N-di(prop-2-yn-1-yl)methanesulfonamide with formaldehyde and sodium azide afforded N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-, N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-N-phenyl-, and N,N-bis{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}trifluoromethanesulfonamides as the major products together with minor 1-(hydroxymethyl)-1H-1,2,3-triazole isomers.     

Nitropyrazoles: XII. Transformations of the 4-Methyl Group in 1,4-Dimethyl-3,5-dinitropyrazole and Cyclization of the Transformation Products

A preparative procedure for the synthesis of 1,4-dimethyl-3,5-dinitropyrazole by nitration of 1,4-dimethylpyrazole was developed. The reaction of 1,4-dimethyl-3,5-dinitropyrazole with dimethoxymethyl- (dimethyl)amine (N,N-dimethylformamide dimethyl acetal) gave (E)-N,N-dimethyl-2-(1-methyl-3,5-dinitropyrazol- 4-yl)ethenylamine. Acid hydrolysis of the latter afforded (1-methyl-3,5-dinitropyrazol-4-yl)acetaldehyde, and the reaction with sodium nitrite in hydrochloric acid led to formation of 2-hydroxymino-2-(1-methyl- 3,5-dinitropyrazol-4-yl)acetaldehyde. The corresponding O-methyloxime and phenylhydrazone reacted with K₂CO₃ to give 6-methyl-4-nitropyrazolo[4,3-d]isoxazole-3-carbaldehyde O-methyloxime and 1-methyl-3-nitro-4-(2-phenyl-2H-1,2,3-triazol-4-yl)pyrazol-5-ol, respectively. Treatment of (1-methyl-3,5-dinitropyrazol-4-yl)-acetaldehyde with benzenediazonium chloride gave (1-methyl-3,5-dinitropyrazol-4-yl)acetaldehyde phenylhydrazone which underwent intramolecular cyclization with replacement of the 5-nitro group by the action of K₂CO₃ in acetonitrile; in the reaction with K₂CO₃ in ethanol, the 5-nitro group was replaced by ethoxy.     

Aromaticity of Bare Iridium Trimers and Ir3M0/+ and $$\rm{Ir}_3M_2^{+/3+}$$ (M = Li,Na, K,and Be,Ca) Bimetallic Clusters

The structural stabilities, bonding nature, electronic properties, and aromaticity of bare iridium trimers \(\rm{Ir}_3^{+/-}\) with different geometries and spin multiplicities are studied at the DFT/B3LYP level of theory. The ground state of the \(\rm{Ir}_3^{+}\) cation is found to be the ³A₂ (C_2v) triplet state and the ground state of the \(\rm{Ir}_3^{-}\) anion the ⁵A₂ (C_2v) quintet state. A detailed molecular orbital (MO) analysis indicates that the ground-state \(\rm{Ir}_3^{+}\) ion (C_2v, ³A₂) possesses double (σ and partial δ) aromaticity as well as the ground-state \(\rm{Ir}_3^{-}\) ion (C_2v, ⁵A₂). The multiple d-orbital aromaticity is responsible for the totally delocalized three-center metal-metal bond of the triangular Ir₃ framework. \(\rm{Ir}_3^{-}\) (C_2v, ¹A₁) structure motif is perfectly preserved in pyramidal Ir₃M^0/+ (C_s, ¹A′) and bipyramidal \(\rm{Ir}_3M_2^{+/3+}\) (C_2v, ¹A₁) (M = Li, Na, K and Be, Ca) bimetallic clusters which also possess the corresponding d-orbital aromatic characters.     

Synthesis and magnetic properties of quasi-unidimensional oxide Sr<Subscript>6.3</Subscript>Rh<Subscript>2.35</Subscript>Mn<Subscript>2.35</Subscript>O<Subscript>15</Subscript>

Attempts of the synthesis in air of complex oxides Sr₃RhMnO_x and Sr₄Rh_1.5Mn_1.5O_x resulted in revealing formation of a new oxide phase Sr_6.3Rh_2.35Mn_2.35O₉ related to quasi-unidimensional family A_3n+3m A′ _n B_3m+n O_9m+6n at n = 1 and m = 1. Its structural characteristics and magnetic properties are studied. X-ray data of the obtained phase is indicated on the basis of trigonal cell (spatial group P321) with the parameters: a 9.6239(4) Å; c ₁ 4.1130(4) Å, c ₂ 2.4946(2) Å. Manganese and rhodium exist in the compound as the cations Mn⁴⁺, Rh³⁺ and Rh⁴⁺, as follows from the data of measuring of magnetic susceptibility in the range 2–300 K.     

Potential energy surface and proton HFI constants of the cyclopentane radical cation

According to the data of UB3LYP/6-31G* and UMP2/cc-pVTZ calculations, the adiabatic potential energy surface of the cyclopentane radical cation is very intricate and combines six types of stationary structures of C _s and C ₂ symmetry. Ten equivalent C _s structures with the totally symmetric electronic state (C _s (² A′)) correspond to global minima. Conformational transitions between the global minima occur along the inversion and pseudorotation coordinates, for each pair of minima the conformational transition occurring in one stage (through the only transition state). The inversion barrier is ～2 kcal/mol; pseudorotation barriers are ～4–8 kcal/mol. The structure of the potential surface provides the interpretation of the EPR data as a result of dynamic averaging over 20 C _s (² A′) and C ₂ (² A) stationary structures.     

Synthesis and bromination/dehydrobromination of <Emphasis Type="Italic">N,N</Emphasis>-diallyltrifluoromethanesulfonamide

The reaction of triflluoromethanesulfonamide with allyl bromide in dimethyl sulfoxide gave N,N-diallyltrifluoromethanesulfonamide which was subjected to bromination with 1 and 2 equiv of bromine. The product of bromine addition to both allyl groups, CF₃SO₂N(CH₂CHBrCH₂Br)₂, was found to exist as a mixture of two diastereoisomers at a ratio of 9: 11. Its dehydrobromination by the action of sodium methoxide was chemoselective with successive elimination of one, two, and three hydrogen bromide molecules to afford N-(2-bromoprop-2-en-1-yl)-N-(2,3-dibromopropyl)trifluoromethanesulfonamide, N,N-bis(2-bromoprop-2-en-1-yl)trifluoromethanesulfonamide, and N-(2-bromoprop-2-en-1-yl)-N-(propadienyl)trifluoromethanesulfonamide, respectively.     

Vanillal Esters in Reaction with 2-Naphthylamine and 1,3-Diketones

Analogs of natural alkaloids of acridone series, derivatives of4-(9-alkyl-11-oxo-7,8,9,10,1,12-hexahydrobenzo[a]acridin-12-yl) and 4-(12-oxo-12H-benzo[f]indeno[1,2-b]quinolin-13-yl)2-ethoxyphenyl carboxylates were synthesized by a three-component condensation of vanillal with 2-naphthylamine and 1,3-cyclohexanedione, dimedone, phendione, or 1,3-indanedione.     

Synthesis and crystal structure of (1<Emphasis Type="Italic">H</Emphasis>-Benzo[<Emphasis Type="Italic">d</Emphasis>]imidazol-2-yl)(3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)methanone (L). complex formation of copper(II) and cobalt(II) chlorides with L

(1H-Benzo[d]imidazol-2-yl)(3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)methanone (L) and its complexes with copper and cobalt chlorides [CuLCl₂] (I) and [CoLCl₂] (II) are synthesized and studied by IR spectroscopy. The structure of molecule L is determined by X-ray diffraction analysis. Molecule L crystallizes as a cis-trans isomer. The dihydroisoquinoline (A) and benzimidazole (B) fragments lie in the mutually perpendicular planes. The N-C bond lengths of fragment A (double bond N(1)-C(1) 1.278(3) Å, ordinary bond N(1)-C(9) 1.490(3) Å) differ noticeably. The N-C bond lengths in fragment B range from 1.327(4) to 1.389(4) Å. The C=O bond is 1.218(3) Å According to the data of IR spectroscopy and X-ray diffraction analysis, complexes I and II are assumed to have different structures with different coordination modes to the metal atom of molecule L: through the imine atoms N(1) and N(2) of fragments A and B in I and through the N(1) atom of the dihydroisoquinoline fragment and the O atom of the carbonyl group in II.