Computer aided chemical design: using quantum chemical calculations to predict properties of a series of halochromic guaiazulene derivatives

Abstract

With the scientific community becoming increasingly aware of the need for greener products and methodologies, the optimization of synthetic design is of greater importance. Building on experimental data collected from a synthesized guaiazulene derivative, a series of analogous structures were investigated with time-dependent density functional theory (TD-DFT) methods in an effort to identify a compound with desirable photophysical properties. This in silico analysis may eliminate the need to synthesize numerous materials that, when investigated, do not possess viable characteristics. The synthesis of several computationally investigated structures revealed discrepancies in the calculation results. Further refined computational study of the molecules yielded results closer to those observed experimentally and helps set the stage for computationally guided design of organic photonic materials. Three novel derivatives were synthesized from guaiazulene, a naturally occurring chromophore, exhibiting distinct halochromic behaviour, which may have potential in a switchable optoelectronic system or combined with a photoacid generator for data storage. The protonated forms were readily excitable via two-photon absorption.

Azulene—A Bright Core for Sensing and Imaging

“…Computational studies have been performed by Belfield et al on analogous fluorescent guaiazulene species. The group were able to refine their computational model to obtain predicted fluorescence spectra which closely matched those obtained experimentally [ 52 ].…”

Azulene-Derived Fluorescent Probe for Bioimaging: Detection of Reactive Oxygen and Nitrogen Species by Two-Photon Microscopy

“…In the specific context of ROS/RNS detection, no reports employing azulene-containing probes have appeared to date. The two-photon fluorescence of azulene 29 and some derivatives 30 has been studied, yet it has never been utilized in any sensing context (although it has been exploited for fluorescence lithography 31 and applications in optical data storage have been suggested 32 ).…”

Characterization of a Bio‐sourced, Fluorescent, Ratiometric pH Indicator with Alkaline pKa

“…The intentional use of fluorophores from biological sources may be a way to comply with Anastas’ and Warner’s 7 th Principle of Green Chemistry: use of renewable feedstock (1). Fluorophore design based on green principles is a rapidly developing field of research; for example, Woodward et al(2) investigated the derivatization of guaiazulene, a halochromic natural product isolated from fungi, for potential use as switchable optical electronics. Using organisms as sources of fluorophores has the potential to relieve the demand for petroleum feedstock in organic synthesis of fluorescent products.…”