Nonlinear Optical Properties and Phototunable Absorption of a Substituted Dihydroazulene-Vinylheptafulvene Pair of Photochromes.

Quantum calculations were used to study UV-vis absorption properties and nonlinear optical characteristics of a variety of substituted dihydroazulene (DHA)/vinylheptafulvene (VHF) photoswitches. The absorption properties are substantially based on the position and nature of the substituent. In general, electron-donating groups cause red shifts compared to the parent compound. Any electron-withdrawing group, on the other hand, would generate a blue shift. Furthermore, the steric effect at some positions is accountable for the loss of planarity and, as a response, a decrease in electronic conjugation within the molecule, which in most cases result in blue shifts in maximum absorption. The purpose of this research is to investigate the influence of substitution at the seven-membered ring of the DHA/VHF system on the absorption spectra and nonlinear optical characteristics of dihydroazulene photoswitches. UV-vis spectra and hyperpolarizability are determined since a prospective photoswitch should have a minimum overlap of absorption spectra from both isomers. Furthermore, the differential in hyperpolarizability between DHA and VHF is critical for practical applications.

Hydrogen Dissociation Reaction on First-Row Transition Metal Doped Nanobelts.

Zigzag molecular nanobelts have recently captured the interest of scientists because of their appealing aesthetic structures, intriguing chemical reactivities, and tantalizing features. In the current study, first-row transition metals supported on an H6-N3-belt[6]arene nanobelt are investigated for the electrocatalytic properties of these complexes for the hydrogen dissociation reaction (HDR). The interaction of the doped transition metal atom with the nanobelt is evaluated through interaction energy analysis, which reveals the significant thermodynamic stability of TM-doped nanobelt complexes. Electronic properties such as frontier molecular orbitals and natural bond orbitals analyses are also computed, to estimate the electronic perturbation upon doping. The highest reduction in the HOMO-LUMO energy gap compared to the bare nanobelt is seen in the case of the Zn@NB catalyst (4.76 eV). Furthermore, for the HDR reaction, the Sc@NB catalyst displays the best catalytic activity among the studied catalysts, with a hydrogen dissociation barrier of 0.13 eV, whereas the second-best catalytic activity is observed for the Zn@NB catalyst (0.36 eV). It is further found that multiple active sites, i.e., the presence of the metal atom and nitrogen atom moiety, help to facilitate the dissociation of the hydrogen molecule. These key findings of this study enhance the understanding of the relative stability, electronic features, and catalytic bindings of various TM@NB catalysts.

Phototunable Absorption and Nonlinear Optical Properties of Thermally Stable Dihydroazulene-Vinylheptafulvene Photochrome Pair.

The UV-vis absorption characteristics and nonlinear optical properties of a series of substituted dihydroazulene (DHA)/vinylheptafulvene (VHF) photoswitches are investigated by applying quantum calculations. Introduction of substituents at the seven-membered ring resulted in significant changes in their absorption properties depending on the nature and position of the substituent. Electron-donating groups at positions 5, 6, 7, and 8 generally exhibited red shifts with respect to the parent compound. However, the steric effect at positions 8a and 4 is responsible for the loss of planarity and conjugation, which generally leads to blue shifts. In contrast, any electron-withdrawing group, particularly at positions 8a and 4, would cause a blue shift. The presence of bulky groups at position 8a results in a loss of planarity and, as a result, a decrease in electronic conjugation within the molecule, resulting in a blue shift in the maximum absorption. When it comes to halogens, the red shift is directly correlated to the nucleophilicity; the higher the nucleophilicity, the larger the red shift. Regarding hyperpolarizability, the charge separation induces higher hyperpolarizabilities for all substituted VHFs compared to the corresponding DHAs, resulting in a much higher NLO response. In addition, for all DHA and VHF, the highest values of hyperpolarizabilities are calculated for 6-substituted systems. Finally, the objective of this detailed theoretical investigation is to continue exploring the photophysical properties of DHA-VHF through structural modifications.