Congeners of Pyrromethene-567 Dye: Perspectives from Synthesis, Photophysics, Photostability, Laser, and TD-DFT Theory

Abstract

In an attempt to develop photostable and efficient BODIPY (PM) dyes for use in liquid dye lasers, three new congeners of widely used laser dye, PM567, were synthesized and their photophysical properties in various organic solvents, laser performances, and photostabilities in a selected solvent, 1,4-dioxane, have been investigated using a frequency doubled Q-switched (10 Hz) Nd:YAG laser at 532 nm. The results of photostability study in nonpolar 1,4-dioxane revealed the remarkable enhancement in stability of the novel dyes compared to that of PM567 as well as improved laser performances. Cyclic voltammetry study strongly supports the observed enhancement in photostability of the novel dyes compared to that of PM567. The observed properties of the novel dyes in relation to those of PM567 have been rationalized by extensive use of DFT and TD-DFT using the B3LYP/6-31G(d) method of theory.

Synthesis of Expanded Hetero 2,6‐Pyrihexaphyrins

“…All the calculations were performed using Gaussian 09 program package . The macrocycles 2–6 in their ground (S0) state were optimized using hybrid functional B3LYP in conjunction with the basis set 6‐31G(d,p) . The minimum energy states for the optimized structures 2–6 were verified by performing frequency calculations on optimized geometries which indicated sum of the imaginary frequencies equal to zero.…”

“…The minimum energy states for the optimized structures 2–6 were verified by performing frequency calculations on optimized geometries which indicated sum of the imaginary frequencies equal to zero. Using same hybrid functional and basis sets the vertical excitation energies and oscillator strengths were obtained for the 50 lowest S 0 →S n transitions at the optimized S 0 state equilibrium geometries using Time Dependent Density Functional Theory (TD‐DFT) . All the computations in the chloroform media were carried out using the Self‐Consistent Reaction Field (SCRF) under the Polarisable Continuum Model (PCM) , …”

The TDDFT Excitation Energies of the BODIPYs; The DFT and TDDFT Challenge Continues

“…The BODIPY pigment and its derivatives are key entities for phototheranostics [1], including photodynamic therapy [2], functional optoelectronic materials [3], such as solar cells [4][5][6] and light emitting diodes [7], and stimuli-responsive materials [8][9][10][11]. In order to understand or predict the optical properties [12,13] of such important chromophore, and notably the lowest energy electronic transition, a very large number of investigations involving computational argumentations were reported but most of the time the correspondence between the calculated position and experimentally observed one turned out to be chronically poor, where differences ranging from 60 to 100 nm were commonly depicted [14][15][16][17][18][19][20][21][22][23][24][25][26][27]. However, on some rare occasions, the comparison between computations and experiments appeared much better [28,29].…”

Synthesis of Phlorin Analogues of Dithiacorrphycene and Their Use as Specific Chemodosimetric Sensors for Fe3+ Ions

“…The functional and basis set for all atoms used for the DFT method were B3LYP and 6‐31G(d,p), respectively . By using the same hybrid functional and basis set, the vertical excitation energies and oscillator strengths were obtained for the 20 lowest S 0 →S n transitions at the optimized S 0 state equilibrium geometries through the TD‐DFT method . All computations in chloroform were carried out by using the self‐consistent reaction field (SCRF) under the polarizable continuum model (PCM) .…”

“…[44] By using the same hybrid functional and basis set, the vertical excitation energies and oscillator strengths were obtained for the 20 lowest S 0 !S n transitions at the optimized S 0 state equilibrium geometries through the TD-DFT method. [45][46][47][48][49][50][51][52][53] All computations in chloroform were carried out by using the self-consistent reaction field (SCRF) under the polarizable continuum model (PCM). [54][55][56] The electronic absorption spectra, including wavelengths, were systematically investigated by using TD-DFT with the PCM on the basis of optimized ground structures.…”