Универзитет у Београду, Технолошко-металуршки факултет
Abstract
U okviru disertacije, sintetisane su tri serije arilazo piridonskih boja: 5-(arilazo)-
3-cijano-1-etil-6-hidroksi-4-metil-2-piridoni, 5-(arilazo)-3-cijano-6-hidroksi-4-metil-2-
-piridoni i 5-(4-arilazo)-3-cijano-6-hidroksi-1-hidroksietil-4-metil-2-piridoni. Predmet
istraživanja je potpuna strukturna i solvatohromna karakterizacija sintetisanih jedinjenja
kombinacijom eksperimentalnih tehnika i kvantno-hemijskih proračuna.
Eksperimentalne metode podrazumevaju rendgensku strukturnu analizu i FT-IR, NMR i
UV-Vis spektoskopiju.
Energija, geometrijske strukture i vibracioni talasni brojevi 5-(metoksi
supstituisanih fenilazo)-3-cijano-1-etil-6-hidroksi-4-metil-2-piridona dobijeni su
kvantno-hemijskim proračunom, korišćenjem B3LYP, M06 i M06-2X modela, a
stabilnost ovih molekula, kao posledica hiperkonjugativnih interakcija i delokalizacije
naelektrisanja, izučavana je pomoću NBO analize. Optimizovane geometrije 5-(arilazo)-
-3-cijano-1-etil-6-hidroksi-4-metil-2-piridona u vakuumu dobijene su pomoću
B3LYP/6-311++G(d,p) metode. UV-Vis apsorpcione energije za ista jedinjenja
dobijene su pomoću vremenski zavisne DFT metode (TD-DFT). Simulacija je izvedena
pomoću četiri modela: B3LYP, CAM-B3LYP, M06-2X i PBE0.
UV-Vis spektralna svojstva jedinjenja i tautomerija detaljno su ispitani u dva
rastvarača i to u etanolu i N,N-dimetilformamidu. Analizirani su UV-Vis apsorpcioni
spektri u različitim rastvaračima i ispitivan je njihov uticaj na položaj apsorpcionih
maksimuma. Takođe, ispitivan je uticaj prirode i položaja supstituenata u fenilnom
jezgru i različitih supstituenata u položaju 1 piridonovog jezgra na apsorpcione spektre.
Za kvantitativnu ocenu uticaja rastvarača na apsorpcione maksimume svih jedinjenja,
primenjeni su principi LSER analize, i to Kamlet-Taft-ov i Catalán-ov model.
Kvantitativna analiza uticaja supstituenata na apsorpcione maksimume 5-(4-arilazo)-3-
-cijano-6-hidroksi-1-hidroksietil-4-metil-2-piridona urađena je pomoću LFER modela i
to primenom Hammett-ove jednačine. Pored toga, LFER model je primenjen i u
ispitivanju uticaja elektronskih efekata supstituenata na 1H and 13C NMR pomeraje,...In this thesis, three series of arylazo pyridone dyes 5-(substituted phenylazo)-3-
-cyano-1-ethyl-6-hydroxy-4-methyl-2-pyridones, 5-(substituted phenylazo)-3-cyano-6-
hydroxy-4-methyl-2-pyridone and 5-(4-substituted phenylazo)-3-cyano-6-hydroxy-1-
-hydroxyethyl-4-methyl-2-pyridone have been synthesized. The purpose of this research
is a combined experimental and theoretical characterization of the synthesised dyes.
Experimental methods include X-ray single-crystal analysis, as well as FT-IR, NMR
and UV-Vis spectroscopy.
Quantum chemical calculations of energies, geometrical structure and
vibrational wavenumbers of 5-(methoxy substituted phenylazo)-3-cyano-1-ethyl-6-
-hydroxy-4-methyl-2-pyridones have been performed using B3LYP, M06 i M06-2X
models. Stability of these molecules arising from hyperconjugative interactions and
charge delocalization has been analyzed using natural bond orbital analysis. Optimized
geometries in vacuum for 5-(substituted phenylazo)-3-cyano-1-ethyl-6-hydroxy-4-
-methyl-2-pyridones have been obtained using B3LYP/6-311++G(d,p) model. UV-Vis
apsorbtion energies have been calculated using TD-DFT using B3LYP, CAM-B3LYP,
M06-2X and PBE0 models.
UV-Vis spectral properties and tautomerism have been throughly investigated in
ethanol and N,N-dimethylformamide. The effects of the nature and the position of the
substituents in phenyl ring on UV-Vis spectra in different solvents have been examined,
as well as the impact of different substituents in the position 1 of pyridone ring.
Furthermore, solvent effects on absorption spectra have been analysed. For quantitative
evaluation of the solvent effects on the UV-Vis absorption maxima, the principles of the
linear solvation energy relationships are used, i.e. models proposed by Kamlet–Taft and
Catalán. Linear free energy relationships are applied to the UV-Vis absorption spectra
and correlation of absorption frequencies with Hammett substituent constants are
performed. Furthermore, the influence of the electronic nature of the substituents on 1H..