Sinteza i fotokemija adamantil-fenil-diazometana

master's thesis

• Title (english): Synthesis and photochemistry of adamantyl phenyl diazomethane
• Author: Kristin Becker
• Mentor: Nikola Basarić (mentor)
• Committee member: Vesna Petrović Peroković (predsjednik povjerenstva)
• Committee member: Davor Kovačević (član povjerenstva)
• Committee member: Morana Dulić (član povjerenstva)
• Committee member: Ivan Kodrin (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2019-01-21, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U okviru ovog rada provedena je sinteza (adamantan-1-il)fenildiazometana (1) i (adamantan-2-
il)fenildiazometana (2) u svrhu istraživanja njihove fotokemijske reaktivnosti i fotofizičkih svojstava.
Fotokemijska reaktivnost ispitana je reakcijama fotolize u otopinama cikloheksana, metanola i
benzena uz pobudu na 300 nm u više pobuđeno singletno stanje. Produkti fotokemijskih reakcija
izolirani su i okarakterizirani spektroskopskim metodoma (1H i 13C NMR, MS). Za spojeve 1 i 2
utvrđeno je da daju produkte preko singletnih i tripletnih karbenskih međuprodukata. Mjerenjem
kvantnih prinosa reakcije uz pobudu koja odgovara populaciji S1 ili Sn utvrđeno je da spojevi reagiraju
iz viših pobuđenih singletnih stanja, suprotno Kashinom pravilu. Nadalje, mjerenjem fluorescencije
spojeva 1 i 2 ustanovljeno je da se spojevi zračenjem deaktiviraju iz viših pobuđenih stanja, također
suprotno Kashinom pravilu. Navedeni rezultati od izuzetne su važnosti jer ukazuju na mijenjanje
paradigmi u razumijevanju jedne od fundamentalnih reakcija u organskoj kemiji, reakcije
fotokemijske eliminacije dušika iz diazoalkana.

Abstract (english)

This master thesis features the synthesis of (adamant-1-yl)phenyldiazomethane (1) and (adamant-2-
yl)phenyldiazomethane (2) and investigation of their photophysical properties and photochemical
reactivity. The photochemical reactivity was investigated by conducting photochemical reactions in
cyclohexane, methanol and benzene solution upon excitation at 300 nm, which corresponds to the
excitation to higher singlet excited state. Products of photochemical reactions were isolated and
characterized by spectroscopic methods (1H and 13C NMR and MS). For compounds 1 and 2 we found out
that they form products via singlet and triplet carbene intermediates. Furthermore, measurement of the
quantum yields of the reaction upon excitation corresponding to S1 and Sn indicated that the compounds
react from higher excited singlet states, contrary to the Kasha rule. Measurement of fluorescence for
compounds 1 and 2 indicated that they deactivate by radiative transitions from higher singlet excited states,
also contrary to the Kasha rule. The findings described in this thesis change the general paradigms of one of
the fundamental organic chemical reaction, the photoelimination of nitrogen from diazoalkanes.

• Keywords: fotokemija; derivati adamantana; fotoeliminacija dušika; karbeni
• Keywords (english): photochemistry; carbenes; derivatives of adamantane; photoelimination of nitrogen
• Language: croatian
• URN:NBN: urn:nbn:hr:217:909111
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2021-01-21
• Created on: 2019-01-25 12:50:20