Preparation, UV-vis, IR, EPR and resonance Raman study of Fe, Ni, Co and Zn dioxolene complexes

An UV-vis, Raman, IR and EPR spectroscopic study was performed for the water soluble complexes of Fe(III), Ni(II), Co(II) and Zn(II) coordinated to dioxolene ligands derived from oxidized dopamine. The complexes were obtained and stabilized at neutral pH by the strong reducing agent sodium thiosulfate. Iron(III) stabilizes the ligand in catecholate form as [Fe(III)(Cat)2]1-, Cat=dopacatecholate, and the divalent metals as dopasemiquinone (SQ): [Ni(SQ)3]1-, [Co(SQ)3]1- and [Zn(SQ)3]1-. The resonance Raman spectra of the solid complexes as [CAT][Ni(SQ)3], [CTA][Co(SQ)3] and [CTA][Zn(SQ)3], CTA is the cetyltrimethylammonium, are very similar to the spectra of the complexes in solution, while the Fe(III) complex is a mixture of two iron complexes, with catecholate or dopasemiquinone ligands.     

From model compounds to extended pi-conjugated systems: synthesis and properties of dithieno[3,2-b:2',3'-d]phospholes

To explore their suitability for applications in molecular optoelectronics and as sensory materials, novel dithieno[3,2-b:2',3'-d]phospholes have been synthesized and their reactivity and properties investigated. An efficient two-step synthesis allowed for a modular assembly of differently functionalized compounds. The dithieno[3,2-b:2',3'-d]phosphole system exhibits extraordinary optoelectronic properties with respect to wavelength, intensity, and tunability. Owing to the nucleophilic nature of the central phosphorus atom, its significant electronic influence on the conjugated pi system can be altered selectively by chemically facile modifications such as oxidation or complexation with Lewis acids or transition metals. All the dithienophosphole species presented show very strong blue photoluminescence with excellent quantum yield efficiencies supporting their potential utility as blue-light emitting components in organic light emitting diodes (OLEDs). Furthermore, depending on the electronic nature of the phosphorus center, the materials exhibit distinctive optoelectronic properties suggesting that the dithieno[3,2-b:2',3'-d]phosphole system may be useful as sensory material. Theoretical calculations, including time-dependent DFT methods, revealed the excellent predictability of the structures and optoelectronic properties of the functionalized dithienophospholes allowing the design of future dithieno[3,2-b:2',3'-d]phosphole-based materials to be "stream-lined". By using tin-functionalized dithienophosphole monomers, a strategy, which involves Stille coupling, towards extended pi-conjugated materials with significantly redshifted optoelectronic properties is also presented.     

Cobalt nanoparticles on charcoal: a versatile catalyst in the Pauson-Khand reaction,hydrogenation, and the reductive Pauson-Khand reaction

[formula: see text] Dispersions of nanometer-sized cobalt particles with very high stability were prepared in charcoal and analyzed by electron microscopy and X-ray analysis. The resulting cobalt nanoparticles on charcoal (CNC) were successfully used as a catalyst for the carbonylative cycloaddition of alkyne, alkene, and carbon monoxide (Pauson-Khand reaction), hydrogenation, and the reductive Pauson-Khand reaction.     

Arylthiazylamides: syntheses, structures, and bonding properties

Air-sensitive, thermally unstable tris(dimethylamino)sulfonium (TAS) salts (3) of the title anions [ArNSN]- have been prepared from corresponding sulfurdiimides Ar-N=S=N-SiMe3 (2) by Si-N bond cleavage with [(Me2N)3S]-[Me3SiF2]- (TASF). They are characterized by low-temperature X-ray crystallography as Z isomers. Because of the very short terminal S-N distance (144.2 (3h)-147.9 (3i)pm) and the relatively long internal S-N distance (158.3 (3i)-160.3 (3c) pm) the [ArNSN]- ions should be regarded as thiazylamides 1b, rare species containing a S triple bond N triple bond. A bonding model is developed and the experimental results are compared with those of restricted Hartree-Fock (RHF), density functional theory (DFT), and M?ller-Plesset second-order (MP2) calculations.     

Nitrosonium complexes of resorc[4]arenes: spectral, kinetic, and theoretical studies

Resorc[4]arene octamethyl ethers 1-3, when treated with NOBF4 salt in chloroform, form very stable 1:1 nitrosonium (NO+) complexes, which are deeply colored. The complexation process is reversible, and the complexes dissociate and bleach upon addition of methanol or water, to give the starting macrocycles. Resorc[4]arenes 1 and 2 are in the same cone conformation, but with different side-chains, whereas 3 possesses a different conformation (chair), while bearing the same side-chain as 2. Kinetic and spectral UV-visible analysis revealed that NO+ interacts with resorc[4]arenes 1 and 2 both outside and inside their basket, leading to complexes with two absorption patterns growing at different rates, one featuring high-energy bands (HEB) within the near-UV zone, and the other one low-energy bands (LEB), attributed to charge-transfer interactions, within the visible range. The presence of ester carbonyl groups in 2 strongly drives the NO+ cation outside the resorcarene. Resorc[4]arene 3 showed a spectral pattern pointing out a clear involvement of the ester moieties in the NO+ entrapping, beside the formation of significant charge-transfer interactions. 1H NMR spectroscopy and molecular modeling clearly supported these findings.     

Dibenzo[c,h][1,5]naphthyridinediones as topoisomerase I inhibitors: design, synthesis, and biological evaluation

Dibenzo[c,h][1,5]naphthyridinediones were prepared via a novel synthetic pathway. The compounds were designed as topoisomerase I (Top1) inhibitors based on the indenoisoquinoline series of drugs. The results of biological evaluation demonstrate that, unlike very closely related dibenzo[c,h][1,6]naphthyridinediones, dibenzo[c,h][1,5]naphthyridinediones retain the Top1 inhibitory activity of similarly substituted indenoisoquinolines.     

Thallium(I) sandwich, multidecker, and ether complexes stabilized by weakly-coordinating anions: a spectroscopic, structural, and theoretical investigation

The reaction of thallium ethoxide with [H(OEt2)2][H2N{B(C6F5)3}2] in diethyl ether afforded [Tl(OEt2)3][H2N{B(C6F5)3}2] (2a), [Tl(OEt2)4][H2N{B(C6F5)3}2] (2b), or [Tl(OEt2)2][H2N{B(C6F5)3}2].CH2Cl2 (2c), depending on the reaction conditions. The dication in the hydrolysis product [Tl4(mu3-OH)2][H2N{B(C6F5)3}2]2.4CH2Cl2 consists of two bridging and two terminal Tl+ ions bound to triply bridging hydroxides. Heating Et2O complexes in toluene afforded [Tl(eta6-toluene)n][H2N{B(C6F5)3}2] (4, n = 2, 3), while C6Me6 addition gave the first thallium-C6Me6 adduct, [Tl(eta6-C6Me6)2][H2N{B(C6F5)3}2].1.5CH2Cl2 (5a), a bent sandwich complex with very short Tl...centroid distances. These arene complexes show no close contacts between cations and anions. Displacement of toluene ligands by ferrocene gave [Tl2(FeCp2)3][H2N{B(C6F5)3}2]2.5CH2Cl2 (6) which contains the multidecker cations [Tl(FeCp2)]+ and [Tl(FeCp2)2]+ in a 1:1 ratio. By contrast, decamethylferrocene leads to electron transfer; the isolable thallium-ferrocene complexes may therefore be viewed as precursor complexes for this redox step. With 18-crown-6 the complexes [Tl(18-crown-6)2][H2N{B(C6F5)3}2] (11a) and [Tl(18-crown-6)][H2N{B(C6F5)3}2].2CH2Cl2 (11b) were isolated. The structure of the latter shows an eight-coordinate thallium ion, where the coordination to the six oxygen donors in equatorial positions is completed by axial contacts to two F atoms of the counter anions. The bonding between thallium(I) and arenes was explored by density-functional theory (DFT) calculations. The optimized geometry of [Tl(tol)3]+ converged to a structure very similar to that obtained experimentally. Calculations on [Tl(C6Me6)2]+ (5b) to establish whether a linear or bent geometry is the most stable revealed a very flat potential-energy surface for distortions of the Ctr(3)-Tl-Ctr(4) angle. Overall, there is very little energetic preference for one particular geometry over another above about 140 degrees , in good agreement with the crystallographic geometry. The calculated Tl-arene interaction energies increase from 73.7 kJ mol-1 for toluene to 121.7 kJ mol-1 for C6Me6.     

Ester dienolate [2,3]-Wittig rearrangement in natural product synthesis: diastereoselective total synthesis of the triester of viridiofungin A, A2, and A4

[structure: see text] An ester dienolate [2,3]-Wittig rearrangement was utilized to access the alkylated citric acid skeleton 6 that is characteristic for the viridiofungins and other members of the alkyl citrate family of secondary natural products. The [2,3]-sigmatropic rearrangement of (Z,Z)-15 provided the rearrangement product (+/-)-syn-16 in moderate yield and with very good diastereoselectivity. A Julia-Kocienski olefination efficiently served to connect the polar head (+/-)-syn-26 with the lipophilic tail (32a-c) of the viridiofungins. Amide formation between the racemic viridiofungin precursors 35a-c and the enantiomerically pure amino acid L-tyrosine methyl ester followed by preparative reversed-phase HPLC provided the isopropyl dimethyl ester of viridiofungin A ((+)-39a), A2 ((+)-39b), and A4 ((+)-39c) as well as the nonnatural diastereomers (-)-38a-c.     

Effective PET and ICT switching of boradiazaindacene emission: a unimolecular, emission-mode, molecular half-subtractor with reconfigurable logic gates

[reaction, structure: see text] We report a unimolecular system functioning as a combinatorial logic circuit for half-subtractor. The emission characteristics can be modulated by chemical inputs, and when followed at two different wavelengths, two functionally integrated logic gates XOR and INHIBIT are obtained. Both logic gates function in the emission mode, and with very large differences in the signal intensity allowing unequivocal assignment of logic-0 and logic-1.     

[4]Cyclo-N-ethyl-2,7-carbazole: Synthesis,Structural, Electronic and Charge Transport Properties

Nanorings, which are macrocycles possessing radially directed π-orbitals have shown fantastic development in the last ten years. Unravelling their unusual electronic properties has been one of the driving forces of this research field. However, and despite promising properties, their incorporation in organic electronic devices remains very scarce. In this work, we aim to contribute to bridge the gap between organic electronics and nanorings by reporting the synthesis, the structural and electronic properties and the incorporation in an organic field-effect transistor (OFET) of a cyclic tetracarbazole, namely [4]cyclo-N-ethyl-2,7-carbazole ( [4]C-Et-Cbz ). The structural, photophysical and electrochemical properties have been compared to those of structurally related analogues [4]cyclo-9,9-diethyl-2,7-fluorene [4]C-diEt-F (with carbon bridges) and [8]-cycloparaphenylene [8]CPP (without any bridge) in order to shed light on the impact of the bridging in nanorings. This work shows that nanorings can be used as an active layer in an OFET and provides a first benchmark in term of OFET characteristics for this type of molecules.     

Hapten synthesis for (+)-6-(2-chlorophenyl)-3-cyclopropanecarbonyl-8,11-dimethyl-2,3,4,5-tet rahydro-8H-pyrido[4',3':4,5]thieno[3,2-f] triazolo[4,3-a][1,4]diazepine (E6123).

(+)-6-(2-Chlorophenyl)-3-cyclopropanecarbonyl-8,11-dimethyl-2,3,4, 5-tetrahydro-8H-pyrido[4',3':4,5]thieno[3,2-f]triazolo[4,3-a] [1,4]diazepine (E6123) is a very potent platelet-activating factor (PAF) receptor antagonist and shows potent anti-PAF activities at the microgram level in a variety of animal models. In order to examine the pharmacokinetics of E6123 at low doses, establishment of a radioimmunoassay is required. On the basis of the metabolic pattern of E6123, we synthesized 6-[2-chloro-4-(3-carboxypropyl) phenyl]-3-cyclopropanecarbonyl-8,11-dimethyl-2,3,4,5-tetrahydro-8H -pyrido[4',3':4,5]thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepine 22 as a potential hapten. In the synthesis of 22, we developed butynyl carbamate as a piperidine ring N-protecting group to prevent possible side reaction, namely oxidation of the methylene at position 2. This protecting group is stable under usual basic and acidic conditions.     

Asymmetric aminolysis of aromatic epoxides: a facile catalytic enantioselective synthesis of anti-beta-amino alcohols

[reaction: see text] The first asymmetric aminolysis of trans-aromatic epoxides with anilines is described. The process affords enantioenriched anti-beta-amino alcohols in up to 99% ee. The complete regio- and diastereoselectivity observed uses commercially available [Cr(Salen)Cl] as a Lewis acid catalyst and in combination with a very simple experimental procedure renders the present reaction a facile and practical tool for the synthesis of chiral nonracemic anti-beta-amino alcohols.     

per-Hydroxylated pillar[6]arene: synthesis, X-ray crystal structure, and host-guest complexation

A per-hydroxylated pillar[6]arene was prepared. Single-crystal X-ray analysis demonstrated that its molecules are arranged in an up-to-down manner to form infinite channels in the solid state. Its host-guest complexation with a series of bispyridinium salts in solution was further investigated. It was found that the per-hydroxylated pillar[6]arene could form a 1:1 complex with paraquat in acetone with an association constant of 2.2 × 10(2) M(-1). This complex is a [2]pseudorotaxane as shown by its crystal structure, which is the first pillar[6]arene-based host-guest complex crystal structure.     

Short‐Range Interactions in Na Coadsorption with CO and O on Ni(111)

The coadsorption of Na with CO and O on Ni(111) is studied by high‐resolution electron energy loss spectroscopy. Experimental evidence for a very short‐range interaction between Na and coadsorbates is reported, in contrast with recent theoretical predictions overestimating nonlocal alkali‐induced effects. Loss spectra show distinct features, as a consequence of different local [CO]:[Na] and [O]:[Na] stoichiometries.     

Highly sensitive sensory materials for fluoride ions based on the dithieno[3,2-b:2',3'-d]phosphole system

[structure: see text]. The newly developed functionalization of an unsubstituted dithieno[3,2-b:2',3'-d]phosphole at the 5,5'-positions gives access to bis(pinacoleboryl) species that can be utilized as sensory materials for fluoride ions. The fluoride-triggered response of the air- and moisture-stable boryl-functionalized dithienophosphole oxide manifests itself in the generation of a new fluorescence emission that can be detected at very low analyte concentrations (ppm) or even with the naked eye upon irradiation with UV light (366 nm).     

Functionalization of alpha,beta-unsaturated esters and ketones: a facile and highly stereoselective one-pot approach to N-protected alpha,beta-dehydroamino acid derivatives

A new, facile, and highly stereoselective protocol toward alpha,beta-dehydroamino acid derivatives has been developed. The one-pot synthesis was very convenient to perform by using the aminohalogenation reaction of alpha,beta-unsaturated esters and ketones followed by treatment with specific bases. Only two [2.2.2] bicyclic organic bases were found to be effective for this transformation. Good yields (58-68%) and excellent Z-selectivity were obtained for 12 examples. [reaction: see text]     

New P-stereogenic triaminophosphines and their derivatives: synthesis,structure, conformational study,and application as chiral ligands

The synthesis, structural, and conformational studies of new P-chiral triaminophosphines, which feature an indolidine and a 1,2,3,4-tetrahydroquinolidine pattern, respectively, are reported. These compounds can feature very different 3D-structures, although they both could be seen a priori as close derivatives of the previously reported 3-phenyl-1,3-diaza-2-phosphabicyclo[3.3.0]octane. The consequences for the use of such compounds and their derivatives in asymmetric metal-catalysis are discussed on the basis of preliminary results in asymmetric cobalt-catalyzed [6+2] cycloaddition.     

Cucurbit[7]uril moving on side chains of polypseudorotaxanes: Synthesis,characterization, and properties

Novel side chain polypseudorotaxanes with cucurbit[7]uril (CB[7]) threaded onto the side chains are synthesized from a water‐soluble polymer and CB[7] in water by simple stirring at room temperature. CB[7] beads could move from the hexyl groups to the benzyl and a part of viologen units in the side chains of polymer when the molar ratio of CB[7] to the monomer reaches from 1 to 2 as shown by ¹H NMR studies, and it is considered that the hydrophobic and charge‐dipole interactions of CB[7] are the driving forces. The sizes of the polypseudorotaxanes with different molar ratio of CB[7] to 4VBVHeP in aqueous solution increase with increasing the molar ratio of CB[7] to 4VBVHeP as found by DLS and resonance light scattering, while the typical cyclic voltammograms and UV–vis data indicate that CB[7] are not threaded in the viologen units of P4VBVHeP, and the oxidation reduction characteristic of the polymer is remarkably affected by the addition of CB[7]. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Complexes of functionalized dipyrido[3,2-a:2',3'-c]-phenazine: a synthetic, spectroscopic, structural, and density functional theory study

The ligands 11-bromodipyrido[3,2-a:2',3'-c]phenazine and ethyl dipyrido[3,2-a:2',3'-c]phenazine-11-carboxylate have been prepared and coordinated to ruthenium(II), rhenium(I), and copper(I) metal centers. The electronic effects of substitution of dipyrido[2,3-a:3',2'-c]phenazine (dppz) have been investigated by spectroscopy and electrochemistry, and some photophysical properties have been studied. The crystal structures of [Re(L)(CO)(3)Cl] (L = ethyl dipyrido[3,2-a:2',3'-c]phenazine-11-carboxylate or 11-bromodipyrido[3,2-a:2',3'-c]phenazine) are presented. Density functional theory calculations on the complexes show only small deviations in bond lengths and angles (most bonds within 0.02 Angstroms, most angles within 2 degrees) from the crystallographic data. Furthermore, the vibrational spectra of the strongest Raman and IR bands are predicted to within an average 6 cm(-1) for the complexes [Re(L)(CO)(3)Cl] and [Cu(L)(triphenylphosphine)(2)]BF(4) (in the 1000-1700 cm(-1) region). Spectroscopic and electrochemical evidence suggest that reduction of the complex causes structural changes across the entire dppz ligand. This is unusual as dppz-based ligands typically have electrochemical properties that suggest charge localization with reduction on the phenazine portion of the ligand. The excited-state lifetimes of the complexes have been measured, and they range from ca. 200 ns for the [Ru(L)(2,2'-bipyridine)(2)](PF(6))(2) complexes to over 2 mus for [Cu(11-bromodipyrido[3,2-a:2',3'-c]phenazine)(PPh(3))(2)](BF(4)) at room temperature. The emission spectra suggest that the unusually long-lived excited states of the copper complexes result from metal-to-ligand charge transfer (MLCT) transitions as they are completely quenched in methanol. Electroluminescent films may be fabricated from these compounds; they show MLCT state emission even at low doping levels [<0.1% by weight in poly(vinylcarbazole) polymer matrix].     

Water-soluble pillar[4]arene[1]quinone: Synthesis,host-guest property and application in the fluorescence turn-on sensing of ethylenediamine in aqueous solution,organic solvent and air

Water-soluble pillar[5]arenes are a class of typical macrocycles and have aroused tremendous attention for its easy to modify, abundant host-guest properties and extensive applications. However, up to now, all the reported water-soluble pillar[5]arenes acted as the host molecules, whereas they failed to be postsynthetically modified, which seriously impeded the development of the pillar[5]arene-based supramolecular chemistry. In this work, a new water-soluble pillar[5]arene, pillar[4]arene[1]quinone, was designed and synthsized with eight quaternary ammonium groups as well as a quinone units. Such a new water-soluble pillar[4]arene[1]quinone was capable of forming 1:1 stable complex with sodium 1-octanesulfonate in aqueous solution. Since the 1,4-quinone unit of WP[4]Q[1] could react with ethylenediamine (EDA) to form a conjugated quinoxaline structure, so pillar[4]arene[1]quinone could apply to the facile fluorescence turn-on sensing of EDA in aqueous solution, organic solvent and air.