Synthesis, Properties, and Solid-State Structures of a Series of 6,13-Dicyanoheteropentacene Analogues: Towards New Liquid Crystalline Materials

The focus of this thesis is the synthesis of novel heterocyclic pentacene analogs and the investigation of their self-organization for the development of new materials for organic electronics. The thesis consists of two interrelated projects: the first being development of an improved synthesis of a series of liquid crystalline dicyanotetraoxapentacenes (DCTOPs) while the second entails the exploratory synthesis of several novel dicyanoheteropentacene analogues and a preliminary investigation of their photophysical properties and solid-state structures. Both of these projects centre around the use of nucleophilic aromatic substitution reactions on tetrafluoroterephthalonitrile. Soluble, tetrakis(bis(alkoxy)phenyl)-substituted DCTOPs were originally synthesised via a short synthesis complicated by a tedious purification required in the last step. Despite this, derivatives bearing long alkyl chains were prepared which displayed liquid crystalline properties in addition to aggregation-induced emission. Building upon this success, but with the goal of achieving DCTOPs in an efficient synthetic manner for this thesis, changes were made which eliminated the troublesome fourfold Suzuki coupling by changing the order of reactions, which in turn required a protection-deprotection sequence. Purification in the new synthesis was greatly simplified and the target tetraaryl-DCTOPs were accessed in good overall yields and purities. The synthesis and solid state structures of these DCTOPs are discussed in Chapter 2. Building on the methods developed in Chapter 2, several novel pentacene analogues containing combinations of nitrogen, oxygen, and sulfur atoms installed within the pentacene core were also synthesised. These compounds were prepared in good yields, and preliminary photophysical studies show that all the compounds displayed luminescence in solution and the solid state. It was also shown that replacement of O with N leads to a red shift in absorption and emission spectra. The X-ray crystal structures show that several of these compounds exhibit π−stacking in the solid state, which is an important design element for applications in organic electronics. The synthesis, photophysical properties, and solid-state organization of these novel 6,13-dicyanoheteropentacene analogues are discussed in Chapter 3

Structure and Magnetic Properties of a 1D Alternating Cu(II) Monomer―Paddlewheel Chain

One-dimensional metal–organic coordination polymers make up a class of compounds with potential towards the development of practical, new magnetic materials. Herein, a rare example of an ABBABB coupled linear chain comprised of alternating dicopper(II) tetraacetate units bridged to copper(II) acetate monomer units via axial η2:η1:µ2 coordinated acetate is reported. Examination of the structure, determined by small molecule X-ray crystallography, shows that each Cu(II) ion is in a dx2–y2 magnetic ground state. Magnetic susceptibility and magnetization data were collected and, consistent with the structural interpretation, demonstrate that the Cu(II) dimer (paddlewheel) exhibits classic antiferromagnetic exchange, while the S = 1/2 Cu(II) monomer is uncompensated in the ground state (low temperature regime.) Data were therefore fitted to a modified Bleaney-Bowers model, and results were consistent with the only other reported chain in this class for which magnetic data are available

Copper(II)- and gold(III)-mediated cyclization of a thiourea to a substituted 2-aminobenzothiazole

Benzothiazole derivatives are a class of privileged molecules due to their biological activity and pharmaceutical applications. One route to these molecules is via intramolecular cyclization of thioureas to form substituted 2-aminobenzothiazoles, but this often requires harsh conditions or employs expensive metal catalysts. Herein, the copper(II)- and gold(III)-mediated cyclizations of thioureas to substituted 2-aminobenzothiazoles are reported. The single-crystal X-ray structures of the thiourea N-(3-methoxyphenyl)-N\u27- (pyridin-2-yl)thiourea, C13H13N3OS, and the intermediate metal complexes aquabis[5-methoxy-N-(pyridin-2-yl-κN)-1,3-benzothiazol-2-amine-κN3]copper(II) dinitrate, [Cu(C13H11N3OS)2(H2O)](NO3)2, and bis{2-[(5-methoxy-1,3-benzothiazol- 2-yl)amino]pyridin-1-ium} dichloridogold(I) chloride monohydrate, (C13H12N3OS)2[AuCl2]Cl⋅H2O, are reported. The copper complex exhibits a distorted trigonal–bipyramidal geometry, with direct metal-to-benzothiazoleligand coordination, while the gold complex is a salt containing the protonated uncoordinated benzothiazole, and offers evidence that metal reduction (in this case, AuIII to AuI) is required for the cyclization to proceed. As such, this study provides further mechanistic insight into the role of the metal cations in these transformations

Aquachlorido(2-{[6-(dimethylamino)pyrimidin-4- yl]sulfanyl}pyrimidine-4,6-diamine)copper(II) chloride hydrate

A copper(II) complex of the non-symmetric bidentate ligand 2-{[6-(di­methyl­amino)­pyrimidin-4-yl]sulfan­yl}pyrimidine-4,6-di­amine (L1) is reported. The single-crystal X-ray structure of aqua­[aqua/chlorido­(0.49/0.51)](2-{[6-(di­methyl­amino)­pyrimidin-4-yl]sulfan­yl}pyrimidine-4,6-di­amine)­copper(II) 0.49-chloride 1.51-hydrate, [CuCl1.51(C10H13N7S)(H2O)1.49]Cl0.49·1.51H2O or [(L1)Cl1.51(H2O)1.49Cu]0.49Cl·1.51H2O, exhibits distorted square-pyramidal geometry around the metal centre, with disorder in the axial position, occupied by chloride or water. The six-membered metal–chelate ring is in a boat conformation, and short inter­molecular S- - -S inter­actions are observed. In addition to its capacity for bidentate metal coordination, the ligand has the ability to engage in further supra­molecular inter­actions as both a hydrogen-bond donor and acceptor, and multiple inter­actions with lattice solvent water mol­ecules are present in the reported structure

Noncommutative geometry, topology and the standard model vacuum

As a ramification of a motivational discussion for previous joint work, in which equations of motion for the finite spectral action of the Standard Model were derived, we provide a new analysis of the results of the calculations herein, switching from the perspective of Spectral triple to that of Fredholm module and thus from the analogy with Riemannian geometry to the pre-metrical structure of the Noncommutative geometry. Using a suggested Noncommutative version of Morse theory together with algebraic $K$-theory to analyse the vacuum solutions, the first two summands of the algebra for the finite triple of the Standard Model arise up to Morita equivalence. We also demonstrate a new vacuum solution whose features are compatible with the physical mass matrix.Comment: 24 page

4-Oxo-1,4-dihydro­benzo[h][1,3]thia­zeto[3,2-a]quinoline-1,3-dicarb­oxy­lic acid

In the title mol­ecule, C16H9NO5S, there is an intra­molecular O—H⋯O hydrogen bond involving the quinolone carbonyl O atom and a carboxyl OH group. In the crystal, inter­molecular O—H⋯O hydrogen bonds between the carbonyl group of the quinolone carboxyl group, and a second carboxyl group on the thia­zeto moiety lead to the formation of chains propagating along [201] and perpendicular to the π-stacks of mol­ecules

DNA Binding of Centromere Protein C (CENPC) Is Stabilized by Single-Stranded RNA

Centromeres are the attachment points between the genome and the cytoskeleton: centromeres bind to kinetochores, which in turn bind to spindles and move chromosomes. Paradoxically, the DNA sequence of centromeres has little or no role in perpetuating kinetochores. As such they are striking examples of genetic information being transmitted in a manner that is independent of DNA sequence (epigenetically). It has been found that RNA transcribed from centromeres remains bound within the kinetochore region, and this local population of RNA is thought to be part of the epigenetic marking system. Here we carried out a genetic and biochemical study of maize CENPC, a key inner kinetochore protein. We show that DNA binding is conferred by a localized region 122 amino acids long, and that the DNA-binding reaction is exquisitely sensitive to single-stranded RNA. Long, single-stranded nucleic acids strongly promote the binding of CENPC to DNA, and the types of RNAs that stabilize DNA binding match in size and character the RNAs present on kinetochores in vivo. Removal or replacement of the binding module with HIV integrase binding domain causes a partial delocalization of CENPC in vivo. The data suggest that centromeric RNA helps to recruit CENPC to the inner kinetochore by altering its DNA binding characteristics

Acetato­aqua­{4,4′,6,6′-tetra-tert-butyl-2,2′-[(2-pyridyl­meth­yl)imino­dimethyl­ene]diphenolato}manganese(III) ethanol solvate

In the title complex, [Mn(C36H50N2O2)(CH3COO)(H2O)]·CH3CH2OH, the MnIII atom is in an octa­hedral environment and is coordinated by the tetra­dentate amine–bis­(phenolate) ligand, a monodentate acetate anion and a water mol­ecule. An ethanol solvent mol­ecule is also found in the asymmetric unit. The structure displays O—H⋯O and C—H⋯O hydrogen bonding

Проблема достоверности научного знания

Знание в самом общем виде можно определить как верное отражение в сознании человека явлений материального и духовного мира и, в частности, многообразных явлений общественной жизни