X-ray, kinetics and DFT studies of photochromic substituted benzothiazolinic spiropyrans.

Photochromic molecules have the potential to find utility in a wide variety of applications including photoswitchable binding and optical memory. This work explores the relationship between photochromism and structural parameters such as particular bond lengths for this class of compounds for which very few crystal structures have been published. Photochemical kinetics, Density Functional Theory (DFT) and X-ray crystallography were used to study the benzothiazolinic spiropyran 3-methyl-6-nitro-3'-methylspiro-[2H-l-benzopyran-2,2'-benzothiazoline]. A second benzothiazolinic spiropyran 3-methyl-8-methoxy-6-nitro-3'-methylspiro-[2H-l-benzopyran-2,2'-benzothiazoline] was synthesized and subjected to photochemical and computational studies. Selected structural and photochemical data for these, related benzothiazolinic spirooxazines and spiropyrans, and related thiazolidinic spiropyrans are compared. Both benzothiazolinic spiropyrans exhibit photochromic properties that are influenced by substituents, solvent, and temperature. The crystallographic C(spiro)-O bond distance of 3-methyl-6-nitro-3'-methylspiro-[2H-l-benzopyran-2,2'-benzothiazoline] that has been shown to correlate with photochromic properties is 1.458 A. The crystallographic C(spiro)-O bond distance matches that of the structure generated by DFT calculations exactly. The effect of substituents on calculated bond lengths and photochemical parameters was determined. For this class of compounds, both X-ray geometry and DFT optimized geometry may be used to predict photochromism, but not degree of photocolorability.