Exploring the potential of anthracene derivatives as fluorescence emitters for biomedical applications.

Two novel anthracene derivatives were synthesized, and detailed photo-physical and biological investigations were carried out using a variety of spectroscopy techniques. The effect of cyano (-CN) substitution was found to be effective to alter the charge population and frontier orbital energy levels via Density Functional Theory (DFT) calculations. Particularly, the introduction of styryl and triphenylamine groups attached to the anthracene core helped to increase the conjugation relative to the anthracene moiety. The results revealed that the molecules have intramolecular charge transfer (ICT) properties, occurring from the electron donating triphenylamine to the electron accepting anthracene moiety in solutions. In addition, the photo-physical properties are strongly cyano-dependent, where the cyano-substituted (E/Z)-(2-anthracen-9-yl)-3-(4'-(diphenylamino)biphenyl-4yl)acrylonitrile molecule showed stronger electron affinity due to the enhanced internal steric hindrance compared to the (E)-4'-(2-(anthracen-9-yl)vinyl)-N,N-diphenylbiphenyl-4-amine molecule, which resulted in a lower photoluminescence quantum yield (PLQY) value and a shorter lifetime in the molecule. Besides, the Molecular Docking approach was used to investigate possible cellular staining targets to confirm cellular imaging potential of the compounds. Moreover, cell viability analyses put forth that synthesized molecules do not exhibit significant cytotoxicity under 125 µg mL-1 concentration on the human dermal fibroblast cell line (HDFa). Moreover, both of the compounds showed great potential in cellular imaging of HDFa cells. Compared to Hoechst 33258, a common fluorescent dye used for nuclear staining, the compounds showed higher magnification of cellular structure imaging capacity by staining the whole cellular compartment. On the other hand, bacterial staining showed that ethidium bromide has higher resolution in monitoring Staphylococcus aureus (S. aureus) cell culture.

Synthesis and investigation of intra-molecular charge transfer state properties of novel donor-acceptor-donor pyridine derivatives: the effects of temperature and environment on molecular configurations and the origin of delayed fluorescence.

A novel series of donor-acceptor-donor (D-A-D) structured pyridine derivatives were synthesised and detailed photo-physical investigations were made using mainly steady-state and time-resolved spectroscopy techniques at varying temperatures. The investigations showed that the molecules have solvent polarity and temperature dependent excited-state configurations, confirmed in two different polarity solvents (295-90 K), i.e. methyl cyclohexane (MCH) and 2-methyltetrahdrofurane (2-MeTHF). In MCH, the investigations revealed dual fluorescence over the temperature range of 295-90 K. At 295 K, the ground-state configuration of the molecules has a partially twisted geometry as determined by DFT calculation, yet the emission originates totally from a locally excited (LE) state, however once the temperature is lowered to 90 K, the twisted molecular configuration is stabilised, and the emission originates from a fully-relaxed intramolecular charge transfer state (ICT), this is contrary to the systems where structural reorganisation stabilises ICT and this is frozen out at low temperatures. The DFT calculations revealed different ground state molecular configurations due to the presence of different electron-donating groups, e.g. the molecule including anthracene groups has a near 90° twisted geometry whereas the triphenylamine including molecule has a pyramidal geometrical folding, therefore, the decrease in temperature restricts the donor degree of rotational freedom. In 2-MeTHF solution, the fluorescence spectrum of both molecules is always of ICT character, but gradually red-shifts through the fluid to glass transition temperature (∼135 K), in this case, the fluorescence occurs after structural and solvent-shell relaxations, however, upon cooling below 135 K, the spectra dramatically shift back to blue giving rise to strong emission from an ICT excited-state (but not the LE state) where the molecules have unrelaxed geometries. This significant change in the nature of the emitting species was explained with specific solvent-solute dynamic interactions in the vicinity of the solvation shell and the effect of thermal excitation of molecular vibrational modes of the C-C bond linking donor and acceptor units. Finally, we confirmed that the molecules have ICT ground-state geometry in the solid-state phase (spin-coated films), and the time-resolved decay dynamics were investigated comparing the spin-coated films (at RT and 25 K) and MCH solutions (at 295 K and 90 K).