Application of -CF-Fluorophore BODIPY with Phenyl and Pyrazolyl Substituents for Lifetime Visualization of Lysosomes.

A bright far-red emitting unsymmetrical -CF-BODIPY fluorescent dye with phenyl and pyrazolyl substituents was synthesized by condensation of trifluoropyrrolylethanol with pyrazolyl-pyrrole, with subsequent oxidation and complexation of the formed dipyrromethane. This BODIPY dye exhibits optical absorption at λ ≈ 610-620 nm and emission at λ ≈ 640-650 nm. The BODIPY was studied on Ehrlich carcinoma cells as a lysosome-specific fluorescent dye that allows intravital staining of cell structures with subsequent real-time monitoring of changes occurring in the cells.

Electronic transitions in noncovalent BODIPY dimers: TD-DFT study.

Theoretical computations have been performed on the absorption spectra of (8-R-TMB) dimers with varying character of substituents at the 8 position (meso) at monomers units (R = NH, OH, CH, H, COH, CF, CN). The obtained results (TD-CAM-B3LYP) show that the first four lower transitions of studied dimers (S → S, i = 1-4) are intrinsically linked with delocalized HOMO and LUMO orbitals of the two monomers, which constitute a dimer. For all the dimers, S → S and S → S transitions are strongly forbidden, whereas S → S and S → S are allowed.

Theoretical Investigation of Carbon Dioxide Adsorption on Li-Decorated Nanoflakes.

Recently, the capture of carbon dioxide, the primary greenhouse gas, has attracted particular interest from researchers worldwide. In the present work, several theoretical methods have been used to study adsorption of CO molecules on Li-decorated coronene (Li@coronene). It has been established that Li can be strongly anchored on coronene, and then a physical adsorption of CO will occur in the vicinity of this cation.

Hydrogen adsorption on inorganic benzenes decorated with alkali metal cations: theoretical study.

Hydrogen adsorption on different benzenes, both organic and inorganic, decorated with Li cations (Li+) was systematically studied by using quantum chemistry techniques. Our calculations demonstrate that Li+-decoration enhances the hydrogen storage ability of the complexes. MP2 calculations reveal that one to five hydrogen molecules per Li+ have high adsorption energies (Ead), up to -4.

Theoretical predictions of the spectroscopic properties of BODIPY dyes: Effects of the fused aromatic and heteroaromatic rings at the b, g bonds.

The fusion of aryl and heteroaryl moieties in the BODIPY skeleton is the important route to design BODIPYs exhibiting absorption and fluorescence in red or near infra-red regions. Despite the importance of this approach, little is known about the influence of aryl and heteroaryl rings on the position of the energy levels of the lower electronic states of such dyes. In this paper, the influence of benzene (B), thiophene (T) and furan (F) rings fused in the BODIPY core (b) at both b and g bonds on the optical properties of the symmetric BbB, TbT and FbF and asymmetric TbF, BbF and BbT dyes have been investigated by TD-CAM-B3LYP and RI-CC2 calculations.

Absorption and fluorescence properties of non-symmetric benzo-, furo-, and thieno-fused structures at the b bonds in the BODIPY frame.

The influence of furo-, thieno-, and benzo-fused structures at the b bonds in the BODIPY frame on the optical properties is investigated by TD-CAM-B3LYP and RI-CC2 calculations. The most important result is that substituents at the b bond of the BODIPY core affect strongly the S-S gaps. In contrast to the S (local excited (LE-type)) state, energy of which is nearly the same for all the substituents at the b bond, energy of the S (charge transfer (CT-type)) state depends strongly on the nature of the substituent and decreases in the following order: furo-fused > thieno-fused > benzo-fused.

Absorption properties of a BODIPY-curved graphene nanoflake system: A theoretical investigation.

Modifications in the electronic transitions of a popular 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (boron dipyrromethene, BODIPY) dye caused by quasi-parallel stacking with corannulene (C) were studied by means of time-dependent density functional theory (TD-DFT) with the CAM-B3LYP functional. The effects of the electron-withdrawing (CN) and electron-donating (NH) substituents at the meso (8) position in the BODIPY core and the corannulene rim position on the character, location, and oscillator strengths (f) of some transitions of complexes were also discussed. To understand better the nature of the transitions, their occupied and virtual orbitals involved into the first electronic transitions as well as the electron density difference plots between excited and ground states of the complexes were investigated.

Optical properties of bilayer quantum dot models based on coronene and its BN analogues with a BODIPY dye: Theoretical TD-CAM-B3LYP-D3 investigation.

Quantum dots (QD) belong to a class of materials considered technologically important for their tunable absorption and emission properties and a huge application potential in optoelectronic technologies. To date, only simplified monolayer models of QDs and their dimers have been considered when modeling their absorption and/or emission spectra and effects of edge functionalization. Here, we analyze the optical properties of new type electron donor-acceptor bilayer quantum dot models based on coronene and its boron-nitride analogues (electron donors) with a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene dye (Bdp, an electron acceptor) dye by using time-dependent density functional theory.

Effect of methyl substituents on the electronic transitions in simple meso-aniline-BODIPY based dyes: RI-CC2 and TD-CAM-B3LYP computational investigation.

The S→S, i=1-5 electronic transitions of four 8-(4-aniline)-BODIPY and four 8-(N,N-dimethyl)-BODIPY dyes, differ by number and position of methyl substituents in the BODIPY frame, were investigated theoretically using ab initio the coupled cluster doubles (CC2) and TD-CAM-B3LYP methods. Methyl substituents in the BODIPY frame and the aniline fragment at the meso position disturb energy of local excitations S→S, S→S, and S→S weakly in comparison with the fully unsubstituted BODIPY molecule. These transitions in experimental spectra form the most long-wave absorption bands at ca.

Effect of meso-substituents on the electronic transitions of BODIPY dyes: DFT and RI-CC2 study.

In this work, the influence of substituents on the electronic transitions of model 8-R-BODIPY dyes (R=NMe2, NH2, OH, CH3, H, F, SH, Cl, Br, CF3, CN, and NO2) was investigated theoretically using time-dependent density functional theory (TD-DFT) and ab initio coupled-cluster doubles (CC2) quantum chemical calculations. Quantum chemical modeling shows a direct relationship between the electron donating and electron withdrawing character of substituents expressed by Hammett substituent constants (σp) and changes in energy of the HOMO-LUMO gap modulating spectral shifts of the S0→S1 transition. Good linear correlations of the calculated LUMO energies and σp as well as the shape of the HOMO and LUMO allow to obtain a reasonable explanation for the observed effects of substituents.