Příprava a vlastnosti nových polymerů substituovaných acetylenů

V rámci předkládané disertační práce byly vyvinuty nové postupy přípravy polyacetylenů s luminescenčně účinnými naftalimidovými skupinami, které mohou najít potenciální využití v optoelektronice a sensorech. Tyto postupy poskytují luminescenční: a) lineární polyacetyleny zpracovatelné z roztoků; b) mesoporézní polyacetylenové sítě s velkým objemem pórů. Rozpustné luminiscentní polyacetyleny byly připraveny dvěma syntetickými cestami: (i) kopolymerizacemi ethynyl derivátů naftalimidu (PN) s ethynylaromáty indukovanými katalyzátorem [Rh(nbd)acac] a (ii) modifikacemi poly(disubstituovaných acetylen)ů obsahujících -chloralkylové skupiny, spočívajícími v nukleofiní substituci chloru za azidové skupiny a následné "click" reakci Huisgenova typu (azido skupin s ethynylovými skupinami PN). PN sice netvoří homopolymery, avšak je možné tento monomer kopolymerizovat s ethynylaromáty, přičemž nejvyšší dosažená molární frakce PN jednotek v kopolymeru je 0.5. Toto pozorování indikuje absenci diád a delších sekvencí PN jednotek v řetězcích kopolymerů. Implikuje tedy alternační strukturu řetězců s ekvimolárním obsahem jednotek. Zajímavé je, že ethynylareny poskytující nerozpustné homopolymery vytvářejí s PN rozpustné kopolymery. Studie provedená na sérii nových diarylacetylenů ukázala negativní efekt strukturní...New procedures for preparation of polyacetylenes with highly luminescent naphthalimide groups that might be potentially utilized in optoelectronics and sensors are developed within the framework of present doctoral thesis. The procedures provide luminescent a) linear polyacetylenes that can be processed from solutions, and b) mesoporous network polyacetylenes with high pore volume. Two paths to soluble polyacetylenes are used: (i) copolymerization of ethynyl- functionalized naphthalimide (monomer PN) and a monoethynyl aromate catalyzed with [Rh(nbd)acac], and (ii) modification of poly(disubstituted acetylene)s carrying -chloroalkyl pendants involving the exchange of chlorine atoms for azido groups and subsequent "click"- reaction of Huisgen type of azido groups with ethynyl groups of PN. The PN does not homopolymerize but copolymerizes with ethynylaromates. The highest possible molar fraction of the PN units in copolymers is of 0.5, which suggests the absence of PN dyads or longer sequences in copolymers and the alternating arrangement of PN units in the copolymers of the composition of 0.5. Surprisingly, ethynylarenes that give insoluble homopolymers gave soluble copolymers with PN. The modification procedure requires knowledge on the effect of the monomer structure symmetry and substituent...Katedra fyzikální a makromol. chemieDepartment of Physical and Macromolecular ChemistryPřírodovědecká fakultaFaculty of Scienc

Synthesis and characterization of new polymers of substituted acetylenes

New procedures for preparation of polyacetylenes with highly luminescent naphthalimide groups that might be potentially utilized in optoelectronics and sensors are developed within the framework of present doctoral thesis. The procedures provide luminescent a) linear polyacetylenes that can be processed from solutions, and b) mesoporous network polyacetylenes with high pore volume. Two paths to soluble polyacetylenes are used: (i) copolymerization of ethynyl- functionalized naphthalimide (monomer PN) and a monoethynyl aromate catalyzed with [Rh(nbd)acac], and (ii) modification of poly(disubstituted acetylene)s carrying -chloroalkyl pendants involving the exchange of chlorine atoms for azido groups and subsequent "click"- reaction of Huisgen type of azido groups with ethynyl groups of PN. The PN does not homopolymerize but copolymerizes with ethynylaromates. The highest possible molar fraction of the PN units in copolymers is of 0.5, which suggests the absence of PN dyads or longer sequences in copolymers and the alternating arrangement of PN units in the copolymers of the composition of 0.5. Surprisingly, ethynylarenes that give insoluble homopolymers gave soluble copolymers with PN. The modification procedure requires knowledge on the effect of the monomer structure symmetry and substituent..

Microporous conjugated polymers via homopolymerization of 2,5-diethynylthiophene

Homopolymerizations of 2,5-diethynylthiophene into conjugated microporous polymers by (i) chain-growth polymerization and (ii) polycyclotrimerization are described. Both methods provide nearly quantitative yields of thiophene-rich (7.6 mmol thiophene rings/g) networks with specific surface area up to 839 m2/g. The thiophene units enhance the affinity of the networks to CO2 and red-shift the UV/vis and fluorescence absorption and emission bands of the networks, respectively. © 2017 Elsevier Ltd15-09637S, GACR, Grantová Agentura České RepublikyCzech Science Foundation [15-09637S]; Ministry of Education, Youth and Sports [NPU I (LO1504)]; Slovak Research and Development Agency APVV [APVV-15-0545

Microporous conjugated polymers via homopolymerization of 2,5-diethynylthiophene

Homopolymerizations of 2,5-diethynylthiophene into conjugated microporous polymers by (i) chain-growth polymerization and (ii) polycyclotrimerization are described. Both methods provide nearly quantitative yields of thiophene-rich (7.6 mmol thiophene rings/g) networks with specific surface area up to 839 m2/g. The thiophene units enhance the affinity of the networks to CO2 and red-shift the UV/vis and fluorescence absorption and emission bands of the networks, respectively. © 2017 Elsevier Ltd15-09637S, GACR, Grantová Agentura České RepublikyCzech Science Foundation [15-09637S]; Ministry of Education, Youth and Sports [NPU I (LO1504)]; Slovak Research and Development Agency APVV [APVV-15-0545