Annual Report on the Activities funded by the Seventh, Eighth and Ninth European Development Funds (EDFS)(2008/C 286/02). OJ 273, 10.11.2008.

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.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