Molecular assembly of polycyanoarenes with silver salts and synthesis of polycyclic aromatic hydrocarbonds
Márquez, Gerardo B.
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This dissertation encompasses the investigation of two distinct subjects. In the first part, which is in the area of molecular self-assembly, the complexation of organonitrile aryl compounds with three different types of silver (I) salts is examined in the solid state. The assembly of 1-(2,2-dicyanovinyl)naphthalene with silver hexafluoroantimonate resulted in a cationic 3D network. Complexation of 4-(2,2-dicyanovinyl)biphenyl with silver tetrafluoroborate and hexafluoroantimonate from benzene generated two similar structures. While the former displays a cationic 3D network, the latter is defined by cationic 2D sheets. Complexation of 9-(2,2-dicyanovinyl)anthracene with silver hexafluoroantimonate from toluene afforded a cationic 2D ribbon, and from benzene, it yielded cationic 2D sheets. These complexes contained solvent bonded to their structures. However, the hexafluoroantimonate ion is nonbonding. The crystal association of 1,4-bis(cyanovinyl)benzene with silver triflate from benzene yielded neutral 2D sheets whose imperfect-rectangular macrocyclic arrangements are interconnected on both sides by bridges of benzene. On the other hand, the assembly of 1,3- bis(cyanovinyl)benzene with silver triflate from benzene afforded a neutral 3D network formed by two interconnected rings. Solvent and triflate counterions are bonded in both complexes. In the second part of this dissertation, the focus was on the synthesis of four linear PAHs containing a perylene center formed by the connection of two substituted fluoranthene units. Our synthetic approach included the elaboration of fluoranthene building blocks (monomers), followed by the coupling of the monomers resulting in dimers, and finally, ring closure of those dimers, which form the target structures. All of the stages were monitored by mass spectrometry, 1H NMR, and 13C NMR spectroscopy. Out of four dimers, only one successfully underwent ring closure. The UV/Vis absorption and fluorescence spectra for the only obtained target compoundevaluated in chloroform showed absorption bands at 318, 352, 518, 558, and 606 nm and emission bands at 615 and 667 nm. The fluorescence quantum yield at 558 nm was φF = 0.21, and at 606 nm was φF = 0.4. Since the differentiation between the targets relies on the substitution pattern, these results suggest that changes in the fluoranthene moiety render changes in the reactivity through the coupling reaction.
Table of Contents
Chapter 1. Introduction and literature review -- Factors that affect self-assembly -- Objectives and synthetic approaches -- Results and discussion -- Summary -- Conclusions -- Experimental section -- Chapter 2. Introduction and literature review -- From planar to highly twisted PAHs -- Methods used for the building of PAHs -- Perylene structures -- Objectives and synthetic approaches -- Results and discussion -- Conclusions -- Experimental section