Sinteza i fotokemija BODIPY spojeva s fenolnim supstituentom na borovom atomu

master's thesis

• Title (english): Synthesis and photochemistry of BODIPY compounds substituted at the boron atom
• Author: Marko Bogomolec
• Mentor: Irena Škorić (mentor)
• Mentor: Nikola Basarić (komentor)
• Committee member: Irena Škorić (predsjednik povjerenstva)
• Committee member: Tatjana Gazivoda Kraljević (član povjerenstva)
• Committee member: Ante Jukić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Chemical Engineering and Technology; Zagreb
• Defense date and country: 2022-09-28, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U ovom radu opisana je sinteza i fotokemija novih derivata BODIPY spojeva 2–7 koji su supstituirani na atomu bora s jednim ili dva fenolna supstituenta. Derivati 6 i 7, imaju jedan, odnosno dva para-acetoksimetilfenolna supstituenta. Hipoteza istraživanja bila je da će osvjetljavanjem spojeva 2–7 vidljivim svjetlom doći do heterolize B–O veze i eliminacije fenolata iz kojih bi u slučaju spojeva 6 i 7 naknadnom eliminacijom acetata nastali kinon-metidi (QM). Fotokemijsko nastajanje QM zanimljivo je radi njihove antiproliferativne aktivnosti. Sintetizirani spojevi okarakterizirani su spektroskopijom 1H i 13C NMR te spektrometrijom masa. Spektroskopska i fotofizička svojstva spojeva 1–7 ispitana su UV-Vis spektroskopijom i stacionarnom i vremenski razlučenom fluorescencijskom spektroskopijom. Fotokemijska reaktivnost ispitana je osvjetljavanjem otopina spojeva 2–7 u metanolu, a produkti metanolize su izolirani i okarakterizirani spektroskopskim metodama. Izolirani produkti ukazuju da osvjetljavanjem dolazi do heterolize B–O veza. Međutim, nije dokazano nastajanje QM. Fotofizička istraživanja dovedena su u vezu s fotokemijskim ispitivanjima kako bi se utvrdilo ovise li kvantni prinosi fluorescencije i eliminacije fenolnih skupina o fotoinduciranom prijenosu elektrona između fenoksi-supstituenta i BODIPY dijelova molekule.

Abstract (english)

This thesis features the synthesis and photochemistry of new BODIPY derivatives 2–7, which are substituted at the boron atom with one or two phenolic substituents. Derivatives 6 and 7, bear one or two para-acetoxymethylphenol substituents, respectively. The hypothesis of the investigation was that the irradiation of 2-7 by visible light would lead to a heterolysis of the B–O bond and elimination of phenolates, which in the case of 6 and 7 would afford quinone methides (QMs) by subsequent elimination of acetate. Photochemical formation of QMs is interesting owing to their antiproliferative activity. The synthesized compounds were characterized by 1H and 13C NMR spectroscopy and high resolution mass spectrometry. Spectroscopic and photophysical properties of 1-7 were investigated by UV-Vis spectroscopy and stationary and time-resolved fluorescence spectroscopy. The photochemical reactivity was probed by performing irradiations of 2-7 in methanolic solutions whereupon methanolysis products were isolated and characterized by spectroscopic methods. Isolated products indicate that the irradiation leads to the heterolysis of the B-O bonds. However, formation of QMs has not been proved. The photophysical investigation was put in connection with the irradiation studies, probing if the quantum yields of fluorescence and elimination of phenolic groups depend on photoinduced electron transfer between phenoxy substituents and BODIPY.

• Keywords: BODIPY spojevi; fotosolvoliza; fotokemija; fotofizika
• Keywords (english): BODIPY compounds; photosolvolysis; photochemistry; photophysics
• Language: croatian
• URN:NBN: urn:nbn:hr:149:273636
• Project: Number: IP-2019-04-8008; Title: Fotokemija: Reakcijski mehanizmi i primjene u organskoj sintezi i biologiji; Title: Photochemistry: Reaction Mechanisms and Applications in Organic Synthesis and Biology; Acronym: PhotoApp; Leader: Nikola Basarić; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: IP
• Study programme: Title: Applied Chemistry - Graduate study; specializations in: Environmental chemistry and green technologies, Advanced materials and technologies, Applied organic chemistry; Course: Applied organic chemistry; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra primijenjene kemije (magistar/magistra primijenjene kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access
• Created on: 2023-03-28 09:02:32