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

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

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

The Milstein Bipyridyl PNN Pincer Complex of Ruthenium Becomes a Noyori-Type Catalyst under Reducing Conditions

Hydrogenation of the dearomatized PNN ligand of the Milstein bipyridyl complex RuH(CO)[PNN] (2) gives a square-pyramidal Ru(II) product RuH(CO)[pPNN] (5). The central ring of the pPNN ligand is a piperidine. A minor byproduct of the hydrogenation reaction is complex 6 which has a dimeric structure made of two Ru(II) fragments each possessing a partly hydrogenated PNN ligand. The structures of 5 and 6 have been elucidated by NMR spectroscopy and X-ray crystallography. The PNN ligand of 2 is also hydrogenated under the conditions of the catalytic dehydrogenative coupling of ethanol to ethyl acetate. No direct evidence of the aromatized dihydride RuH2(CO)[PNN] (4) was found in this study. However, treating RuHCl(CO)[PNN] with Li[HBEt3] or reacting 2 with H2 at low temperature resulted in a structurally characterized hydride-bridged dimer (7) bearing intact aromatized bipyridyl ligands. M06-L/def2-QZVP DFT calculations provided insights into the thermodynamics of the stoichiometric reactions of this work and into the nature of the intermediates of the catalytic ester hydrogenation facilitated by RuH2(CO)[pPN(H)N] (8) formed from 5 under H2

[2,2′-Imino­diethano­lato(2−)-κ3 O,N,O′][4-(meth­oxy­carbonyl­meth­yl)phen­yl]boron

The title compound, C13H18BNO4, was readily obtained from the reaction of methyl 4-boronobenzene acetate with ethano­lamine. A combination of inter­molecular N—H⋯O hydrogen bonds and C—H⋯π inter­actions leads to the pairwise association of mol­ecules

Supramolecular Interactions Involved in the Solid State Structure of N,N\u27-[bis(pyridin-2-yl)formylidene]ethane-1,2-diamine

The structure of the symmetrical Schiff base, N,N\u27-[bis(pyridin-2-yl)formylidene]ethane-1,2-diamine (bpfd) has been characterized by single crystal X-ray diffraction. The non-covalent supramolecular chemistry involved in the crystal structure of this ligand has been carefully investigated. The structure adopted different motifs of nitrogen-hydrogen interactions that led to the formation of centrosymmetric dimers. In addition, edge-edge and face-face nitrogen-nitrogen interactions were ob-served and reported. The Schiff base (bpfd) ligand crystallizes in a monoclinic space group C12/c1 with a = 19.128(2) Å; b = 5.8776(6) Å; c = 13.1403(15) Å; α = 90o; β = 121.970o(4); γ = 90o and z = 4. This structure is an example of compounds with many symmetry-independent molecules in the asymmetric unit cell (Z > 2)