Synthesis, photochemical and luminescent properties of (E)-2-(2-hydroxyarylethylene)-3-phenylquinazolin-4(3H)-ones

Abstract

Photoinduced transformations of 2 styrylquinazolinones in solutions were studied using absorption and NMR spectroscopy methods. A possibility of control of the photochemical isomerization rate of quinazolinone 2 (hydroxyaryl)ethenyl derivatives by changing the pH of the medium was demonstrated. The bases and the solvent nature also affect the luminescence intensity of solutions of these compounds in the wavelength range of 550-650 nm. The differ ences in the steric organization of the ortho hydroxystyryldiazinone system in crystals and in solutions related to the turn of the aryl group were found. Their influence on the competing processes of luminescence and photochemical transformation of the ethylene fragment were shown. The fact of reversible photo/thermal E-Z isomerization was established for (E) 2 (2 hydroxystyryl) 3 phenylquinazolin 4(3H) one.Key words: (E) 2 styrylquinazolin 4(3H) ones, ortho hydroxystyrylquinazolinones, lumi nescence, reversible photo/thermal isomerization, photoswitching.Diarylethenes and their heterocyclic analogues form the basis of modern electroluminescent and photochro mic materials, successfully used in nonlinear optics, lasers with tunable frequency, optoelectronic devices for record ing and storage of information, molecular photoswitch es. 1,2 Among hetarylstilbenes, their unsymmetric deriva tives 3,4 are of particular interest. Owing to the contribu tion of the n,* state, the presence of an acceptor azine (azinone) core in addition to the donor (aryl) one in stil bene molecules can have a considerable influence on photochemical and photophysical behavior of the lumi nophores. 5 However, there are fewer publications on the studies of the corresponding systems than of the symmetric (het)arylethenes. 4 In particular, there are several works on the synthesis of (E) 2 styrylquinazolin 4(3H) ones and the study of their photophysical properties. 4,6-10 It should be noted that compounds of this type with a specific emis sion ability and a tendency to a photoinduced E-Z iso merization 9,10 can be quite promising for the development of pH sensitive photochromic materials. We think that the introduction of a hydroxy group at the ortho position of the arylethenyl fragment of quinazolinones can gener ate photocontrolled processes related to the E-Z isomer ization with a proton transfer in the course of tautomeric transformations and heterocyclization to the correspond ing spiropyrans. ExperimentalIR spectra were recorded on a Perkin Elmer Spectrum One IR Fourier transform spectrometer using a diffuse reflectance sampling accessory (DRA). Electron absorption spectra were recorded on a UV 2401 PC double beam spectrophotometer (Shimadzu, Japan) in the range of 190-700 nm with the wave length setting accuracy of ±0.3 nm using a Shimadzu Scan stan dard program. Fluorescence spectra were recorded on a Varian Cary Eclipse fluorescence spectrophotometer with mutually per pendicular beams, the wavelength setting accuracy of 0.5 nm. The measurements were carried out in the range of 190-800 nm in SUP...

Crystal structure of 3-(4-hydroxyphenyl)-2-[(E)-2-phenylethenyl]quinazolin-4(3H)-one

“…The phenyl (C21-C26) and the 4-hydroxyphenyl (C12-C17) rings are inclined to one another by 78.2 (2) , and to the quinazolone ring (N1/N2/C2/C4-C10) by 26.44 (19) and 81.25 (8) , respectively. A similar styrylquinazolinone conjugation system geometry has been found in structures reported previously (Trashakhova et al, 2011;Ovchinnikova et al, 2014).…”

“…Fig. 4) gave only three hits:Nosova et al (2012);Trashakhova et al (2011);Ovchinnikova et al (2014). However, none of the characterized single crystals contains a hydrogen-bond donor/acceptor in the aryl substituent at position 3 of the quinazolinone unit and information on intermolecular interactions of such structures is still missing.…”

Photochemical anti–syn isomerization around the –N–N bond in heterocyclic imines

“…[27][28][29] Recently, photochemically-induced isomerization of a quinazolinone derivative containing a large p-system (consisting of two C 6 rings linked by a reduced quinazolinone moiety and a N ring -N]CH-C aromatic bridge) has been described. 30 Unlike previous studies describing isomerization around a C-C linkage [27][28][29] or a N]N linkage (in the case of azobenzene and its derivatives), 31,32 isomerization proceeded around a N-N linkage in the N-N]CH array of this system. This nding prompted us to study similar molecular systems, and in this paper we present experimental data and in-depth theoretical analysis to identify the excited states that are likely to be involved in the photochemically-induced isomerization process.…”

Spectroscopic Studies of Photochemical Transformations of Cymantrenylquinazolinone Derivatives

“…The fluorescence spectra of dicarbonyl chelate 9 , compound 3 , and the organic analogue trans ‐3‐phenyl‐2‐(2‐phenylethenyl)‐3 H ‐quinazolin‐4‐one ( S ) are presented in Figure . It is seen that a sharp increase in the fluorescence intensity is observed for chelate 9 in comparison with tricarbonyl 3 and organic analogue S ; thus, 9 is a better fluorofore than 3 and S .…”

“…In the last decades, compounds with photochromic properties have attracted considerable attention for the creation of devices for the registration and storage of optical information, molecular switches, chemical sensors, and reagents for fluorescence spectroscopy , . It is known that 2‐aryl(hetaryl)‐ and 2‐styrylquinazolinones show distinctive fluorescence properties and therefore have potential for the creation of non‐linear optical generators . Variation of the structures, namely, the substituents in the heterocyclic and aryl fragments, allows one to obtain optical systems with various spectral parameters .…”