Sinteza, karakterizacija i konformacijska analiza novih derivata aromatskih trinitrozo i azo spojeva

master's thesis

• Title (english): Synthesis, characterization and conformational analysis of new derivatives of aromatic trinitroso and azo compounds
• Author: Mateja Pisačić
• Mentor: Ivana Biljan (mentor)
• Mentor: Ivan Kodrin (mentor)
• Committee member: Ivana Biljan (predsjednik povjerenstva)
• Committee member: Ivan Kodrin (član povjerenstva)
• Committee member: Marijana Đaković (član povjerenstva)
• Committee member: Snežana Miljanić (član povjerenstva)
• Committee member: Vesna Petrović Peroković (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2017-09-19, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U sklopu ovog rada provedena je sinteza, karakterizacija i konformacijska analiza novih derivata
aromatskih trinitrozo i azo spojeva. Aromatski trinitrozo spoj pripravljen je reakcijom redukcije iz
odgovarajućeg trinitro spoja te su IR spektroskopijom proučene fototermičke reakcije polimernog
oblika u čvrstom stanju pri kriogenim uvjetima. Kinetika polimerizacije monomernog oblika trinitrozo
spoja u čvrstom stanju, pripravljenog kriogenom fotodisocijacijom polimera, praćena je vremenski
razlučenom IR spektroskopijom. Aromatski azo spojevi priređeni su Millsovom reakcijom između
aromatskog trinitrozo spoja i aromatskih diamino spojeva te aromatskog triamino spoja i aromatskih
dinitrozo spojeva. Pripravljeni spojevi karakterizirani su IR spektroskopijom te difrakcijom
rentgenskih zraka na praškastom uzorku.
Dobiveni produkti proučavani su metodama računalne kemije. Na modelnim spojevima s
azodioksidnom i azo vezom odabrane su molekularno i kvantno-mehaničke metode koje dobro
reproduciraju njihove eksperimentalno određene geometrije. Provedena je pretraga konformacijskog
prostora pretpostavljenih modela novosintetiziranih spojeva kojom su analizirane njihove optimizirane
geometrije. Dane su smjernice za daljnji dizajn sličnih spojeva.

Abstract (english)

Synthesis, characterization and conformational analysis of new derivatives of aromatic trinitroso and
azo compounds was performed. Aromatic trinitroso compound was prepared by reduction of trinitro
derivative, and solid-state cryogenic photothermal reactions of polymeric form were studied by IR
spectroscopy. Kinetics of solid-state polymerization of monomeric trinitroso compound, produced by
cryogenic photodissociation of polymer, was monitored by time-resolved IR spectroscopy. Aromatic
azo compounds were synthesized by Mills reaction between aromatic trinitroso compound and
aromatic diamino derivatives, and aromatic triamino compound and aromatic dinitroso derivatives.
Compounds were characterized by IR spectroscopy and powder X-ray diffraction.
The products were investigated by computational chemistry methods. Models with azodioxide
and azo bonds were used to find molecular and quantum-mechanical methods enabling reproduction
of the experimentally determined geometries. Conformational space search of the assumed models of
new compounds was performed and the obtained geometries were analyzed. Guidelines for future
design of similar compounds were provided.

• Keywords: aromatski azo spojevi; aromatski C-nitrozo spojevi; čvrsto stanje; fototermičke reakcije; kinetika; konformacijska analiza
• Keywords (english): aromatic azo compounds; aromatic C-nitroso compounds; conformational analysis; kinetics; photothermal reactions; solid state
• Language: croatian
• URN:NBN: urn:nbn:hr:217:616454
• 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: 2018-09-19
• Created on: 2017-09-21 09:03:59