Substituent Effects on Thermal Decolorization Rates of Bisbenzospiropyrans

Lu, Nina T.; Nguyen, Vi Nu Hoai; Kumar, Satish; McCurdy, A. K.

doi:10.1021/jo051449j

Cited by 30 publications

(24 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Similar short contacts were reported in the crystal structure of a related compound 3-ethyl-8-methoxy-6-nitro-2H-1-benzopyran-2-spiro-2′-(3′-methylthiazolidine) ( 4 ) by Miler-Srenger et al [26]. However, the crystal structures of two benzothiazolinic spirooxazines (3-methyl-2,3-dihydro-l,3-benzothiazolespiro-2,2′-(3-methyl-2H-phenanthr[9,10-b] [ 1,4]oxazine) ( 5 ), 3-methyl-2,3-dihydro-1,3-benzothiazolespiro-2,2′-(3-methyl-2H-naphth[2, I-b][ 1,4]-oxazine) ( 6 ) reported earlier by Sun et al [26] show no short intermolecular contacts, possibly due to the absence of electron donating or withdrawing substituents. Compound 2 did not crystallize well.…”

Section: Resultsmentioning

confidence: 99%

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

Kumar

Velasco

McCurdy

2010

Journal of Molecular Structure

Self Cite

View full text Add to dashboard Cite

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 Å. 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.

show abstract

Section: Resultsmentioning

confidence: 99%

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

Kumar

Velasco

McCurdy

2010

Journal of Molecular Structure

Self Cite

View full text Add to dashboard Cite

show abstract

“…Spiropyran (SP) systems are well-known chromophores that reversibly photoisomerize to the conjugated merocyanine (MC) moieties, [1][2][3][4] which are attractive candidates for designing devices for optical switching and storage, sensors, cell imaging, etc. [5][6][7][8][9] SP absorbs light in the wavelength range of 200-400 nm to induce bond-cleavage producing the open form MC (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

Energetic and structural properties of different conformations of merocyanine and its protonated forms

Singh

Böhm

Balasubramanian

2015

Chemical Physics Letters

View full text Add to dashboard Cite

We investigate the conformational stabilities, dipole moments, bond lengths and partial charges of photo-sensitive spiropyran (1′,3′-dihydro-1′,3′,3′-trimethyl-6-nitro-spiro[2H-1-benzopyran-2,2′-[2H]indole]) after its photo-switching to the open form conformers, merocyanine and its protonated counterparts. Two approaches, an ab initio Hartree-Fock method supplemented by the Møller-Plesset second-order perturbation theory and density functional theory under B3LYP parameterization, are employed with extended basis sets to examine the energetic ordering of the conformers in vacuum and in an aqueous environment. The influence of the solvent on the conformers is demonstrated by the notable changes in the structural and electrostatic properties.

show abstract

“…The substituent and solvent effects on the photochromic properties of bisbenzospiropyran have been reported 4. The metal binding affinities of three metal ions with the water soluble compound 1a were determined by NMR and reported in a preliminary letter 5.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and metal complexation properties of bisbenzospiropyran chelators in water

Kumar¹,

Chau²,

Chau³

et al. 2008

Tetrahedron

Self Cite

View full text Add to dashboard Cite

As a step towards developing a light-controlled reversible binding switch based on photochromic bisbenzospiropyran for investigating intracellular calcium signaling, substituted bisbenzospiropyran and phenolic chelators were synthesized and examined for metal binding strength. The complexation of these compounds with alkaline earth and zinc ions in methanol and buffer was characterized using NMR and luminescence spectroscopy. An increased length of convergent ligands on the rigid scaffold maintained binding affinity for Ca 2+ but decreased selectivity for Ca 2+ over Mg 2+ . Results indicate that at least three carboxylate ligands are required for significant binding, and increased length of the ligands will result in a fully water-soluble photoswitch that exhibits two states with approximately 300-fold difference in binding affinity for Ca 2+ .

show abstract

Substituent Effects on Thermal Decolorization Rates of Bisbenzospiropyrans

Cited by 30 publications

References 24 publications

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

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

Energetic and structural properties of different conformations of merocyanine and its protonated forms

Synthesis and metal complexation properties of bisbenzospiropyran chelators in water

Contact Info

Product

Resources

About