Spectroscopic and Time-Dependent DFT Study of the Photophysical Properties of Substituted 1,4-Distyrylbenzenes

Abstract

In this contribution, we examine the photophysical properties of 15 totally trans–trans 1,4-distyrylbenzene derivatives (DSBs) functionalized with different electron-donating (ED) and electron-withdrawing (EW) groups by experimental and computational methodologies. We use UV–vis and fluorescence spectroscopies to determine the experimental optical properties such as the maximum absorption (λabs exp) and emission (λem exp) wavelengths, the highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) energy gaps (ΔE abs exp), the molar extinction coefficients (ε), the fluorescence quantum yields (Φf), and the fluorescence lifetimes (τ). We also calculate the experimental spontaneous emission decay rate (k r exp) and correlate all of these magnitudes to the corresponding calculated properties, maximum absorption (λabs cal) and emission (λem cal) wavelengths, vertical transition energies (ΔE abs cal), oscillator strength (F osc), and spontaneous emission decay rate (k r cal), obtained by the time-dependent density functional theory method. We analyze the effect of the electronic nature of the substituents on the properties of the DSBs, finding that the ED and EW groups lead to bathochromic shifts. This is consistent with the decrease of ΔE values as the strength of ED and EW substituents increases. We find excellent correlations between calculated and experimental values for λabs, λem, and ΔE abs (r ∼ 0.99–0.95). Additionally, the correlations between the relative ε with F osc values and the k r values are in good agreement (r ∼ 0.88–0.72) with the experimental properties. Overall, we find that for substituted 1,4-DSBs, computational chemistry is an excellent tool to predict structure–property relationships, which can be useful to forecast the properties of their polymeric analogues, which are usually difficult to determine experimentally.

Size Effect of Arylenediimide π-Conjugate Systems on the Photoresponsive Behaviors in Eu3+-Based Coordination Polymers

“…The normalized electronic absorption spectra are calculated through time-dependent density functional theory for the two ligands, which are in well agreement with the experimental data. As shown in Figure S5, the maximum absorption peak of H 4 BINDI appears at 375 nm because of the π···π* transition, while that of H 4 BIPMDI is observed at 276 nm because of the n···π* transition . Therefore, energy transformations will occur at distinct pathways in H 4 BINDI and H 4 BIPMDI.…”

“…As shown in Figure S5, the maximum absorption peak of H 4 BINDI appears at 375 nm because of the π•••π* transition, while that of H 4 BIPMDI is observed at 276 nm because of the n•••π* transition. 41 Therefore, energy transformations will occur at distinct pathways in H 4 BINDI and H 4 BIPMDI.…”

A novel donor–π–acceptor halochromic 2,6-distyrylnaphthalene chromophore: synthesis, photophysical properties and DFT studies

“…Yellow solid; mp 213-215 C. IR (KBr): 3749, 3441, 1851. 5,1419,1304,1165,1134,1103,964,818,763 .0 mg) and it was evacuated and backlled with argon. Then 5 mL of dry DMF was added to the reaction mixture under fellow of argon and tube was sealed with a screw-cap and the resulting mixture was heated in an oil bath at 120 C for 12 h. Aer completion of the reaction, the mixture was ltered (in hot form) and the remaining solid was washed with DMF (2 mL) in order to separate the catalyst.…”

“…The synthesis of uorophores incorporating distyrylbenzene pconjugated systems has attracted considerable attention because of their high potential applications in optoelectronic and sensory devices as well as uorescent probes in medical utilization and in organic light-emitting diodes. [1][2][3][4][5][6] On the other hand, organic molecules that possess intramolecular charge transfer (ICT) character are important in a large number of areas, such as organic solar cells, polarity probes and nonlinear optics. 7,8 Donor-p-acceptor (D-p-A; where D is an electron-donating group, A is an electron-accepting group, and p is a conjugating moiety) systems with different congurations have been extensively developed because their absorption spectra and energy gaps can be readily tuned by controlling the ICT character using different electron-donor and electron-acceptor groups.…”

Mechanistic insights into the thermal transformations of heterocyclic o-distyrylbenzenes: an experimental and computational study

“…DFT methods have previously proven to be very successful in computing structural and spectroscopic properties of the similar compounds. [21][22][23][24][25][26][27][28][29][30][31] For the first time, we calculated the free energy profiles for the most favorable reaction pathways for the reactions considered above, thus providing an explanation for the experimental observations concerning the thermal reaction of furyl and thienyl o-divinylbenzenes (I-II, VII-VIII and 1-4) under acidic conditions. The intriguing issue of lack of reactivity of some starting precursors to obtain indane/indene products or phenantrene products, or in some cases both of them, was addressed, by (a) revealing the protonation preference of the systems under consideration, which appears to be a reaction-determining factor to produce indane/indene derivatives and (b) giving insights into the energetic requirements and formed product concerning the starting [4+2] cycloaddition step being crucial for reactions to proceed towards fenantrene products.…”