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Preparation and study of a series of diketopyrrolopyrrole (DPP)-based polymers as photoactive substances
Solanský, Lukáš ; Richtár, Jan (referee) ; Cigánek, Martin (advisor)
The present diploma thesis deals with polymers based on organic pigments, their preparation, characterization and use as photoactive substances with a focus on artificial photosynthesis. The experimental part is devoted to the preparation of diketopyrrolopyrrole (DPP) based polymers. 7 DPP derivatives with 5 different side chains were prepared. The preparation of DPP polymers by Stille cross-coupling reaction and direct arylation were compared. Due to the higher efficiency and lower complexity of direct arylation, this polymerization method was used to prepare a series of 20 polymers consisting of a combination of 5 DPP derivatives and 4 comonomers. In the synthesis of several of the resulting polymers, the formation of an insoluble moiety was observed which could not be characterized by available methods, and even the subsequent application of such materials is not possible due to this. On the basis of the data obtained, it became apparent that in particular the bulky adamantane group and the comonomer tetrafluorobenzene were not suitable for the preparation of polymers, as they resulted in very limited soluble materials which, moreover, had a low degree of polymerization. In contrast, polymers containing butyl-TEG, octadecane, the comonomer thiophene and partially benzothiadiazole had degrees of polymerization in the range of 10-33 and exhibited excellent spectral and optoelectric properties. Tests of photocatalytic hydrogen evolution using DPP polymers are under development, but hydrogen was not demonstrably detected in initial measurements on selected polymer materials (P14 and P20).
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Direct arylation and its application in supramolecular polymer synthesis
Loukotová, Lenka
This thesis is divided into two parts. In the first part there is reported palladium- catalysed regioselective direct arylation of benzofurans with arylsulfonyl chlorides as the coupling partner to C2 carbon. The best reaction conditions of this reaction were investigated, then the influence of various arylsulfonyl chloride substituents to the reaction and finally it is reported direct arylation of C2-arylated benzofuran to C3 carbon to give diarylated benzofuran with different aryl substituents. In the second part, there is reported the synthesis of 2-(hydroxymethyl)-5,7-bis{5- [(2,2':6',2''-terpyridine)-4'-yl]thiophen-2-yl}-2,3-dihydrothieno[3,4-b][1,4]dioxin and modification of its sidechain. As a starting material of the synthesis it was used commercially available 4'-bromo-(2,2':6',2''-terpyridine). The synthetic sub-steps included Suzuki cross- coupling, bromination and C-H bond activation. Then it was also reported the complexation of synthesized oligomer with zinc and iron cations.
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Direct arylation and its application in supramolecular polymer synthesis
Loukotová, Lenka
This thesis is divided into two parts. In the first part there is reported palladium- catalysed regioselective direct arylation of benzofurans with arylsulfonyl chlorides as the coupling partner to C2 carbon. The best reaction conditions of this reaction were investigated, then the influence of various arylsulfonyl chloride substituents to the reaction and finally it is reported direct arylation of C2-arylated benzofuran to C3 carbon to give diarylated benzofuran with different aryl substituents. In the second part, there is reported the synthesis of 2-(hydroxymethyl)-5,7-bis{5- [(2,2':6',2''-terpyridine)-4'-yl]thiophen-2-yl}-2,3-dihydrothieno[3,4-b][1,4]dioxin and modification of its sidechain. As a starting material of the synthesis it was used commercially available 4'-bromo-(2,2':6',2''-terpyridine). The synthetic sub-steps included Suzuki cross- coupling, bromination and C-H bond activation. Then it was also reported the complexation of synthesized oligomer with zinc and iron cations.
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Direct arylation and its application in supramolecular polymer synthesis
Loukotová, Lenka ; Svoboda, Jan (advisor) ; Drahoňovský, Dušan (referee)
This thesis is divided into two parts. In the first part there is reported palladium- catalysed regioselective direct arylation of benzofurans with arylsulfonyl chlorides as the coupling partner to C2 carbon. The best reaction conditions of this reaction were investigated, then the influence of various arylsulfonyl chloride substituents to the reaction and finally it is reported direct arylation of C2-arylated benzofuran to C3 carbon to give diarylated benzofuran with different aryl substituents. In the second part, there is reported the synthesis of 2-(hydroxymethyl)-5,7-bis{5- [(2,2':6',2''-terpyridine)-4'-yl]thiophen-2-yl}-2,3-dihydrothieno[3,4-b][1,4]dioxin and modification of its sidechain. As a starting material of the synthesis it was used commercially available 4'-bromo-(2,2':6',2''-terpyridine). The synthetic sub-steps included Suzuki cross- coupling, bromination and C-H bond activation. Then it was also reported the complexation of synthesized oligomer with zinc and iron cations.
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