Synthesis, IR, UV/vis-, 1H NMR and DFT study of chelatophore functionalized 1,3-benzoxazinone spiropyrans

Bulanov, A. O.; Попов, Л. Д.; Shcherbakov, I. N.; Коган, В. А.; Barachevsky, V. А.; Lukov, V. V.; Borisenko, S. N.; Tkachenko, Yu. N.

doi:10.1016/j.saa.2008.03.014

Cited by 15 publications

(8 citation statements)

References 17 publications

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“…Recently, there has been an exponential growth of interest in photochromism for profitable applications in important technologies [1][2][3][4][5][6][7][8][9][10][11][12][13]. Spiropyrans are one of the major classes of organic photochromes [2,3].…”

Section: Introductionmentioning

confidence: 99%

“…The photochromism of the spiropyran/trans-merocyanine pair has been reviewed previously [3]. The rate and mechanism of the reaction of some spiropyrans and their analogues in different media have been examined with different spectroscopic techniques [4][5][6][7][8][9][10][11][12][13][14]. Spiropyran photoisomerization was studied using ion mobility-mass spectrometry and three major conformers were identified.…”

Section: Introductionmentioning

confidence: 99%

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A New Approach for Studying Bond Rupture/Closure of a Spiro Benzopyran Photochromic Material: Reactivity Descriptors Derived from Frontier Orbitals and DFT Computed Electrostatic Potential Energy Surface Maps

Abdel‐Mottaleb

Ali

2016

International Journal of Photoenergy

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This paper focuses on computations technique within the framework of the TD-DFT theory for studying the relationship between structure-properties of reversible conversion of photochromic materials. Specifically, we report on 1′,3′-dihydro-8-methoxy-1′,3′,3′-trimethyl-6-nitrospiro[2H-1-benzopyran-2,2′-(2H)-indole] (SP) and its isomers. TD-DFT calculated UV-Vis electronic spectra of the closed and open isomers of this photochromic material are in excellent agreement with the experimental results. Moreover, this paper reports on the results of theoretical investigations of reactivity indices that may govern the conversion between spiropyrans and its isomers. In addition, the solvent and rigidity of the medium significantly control the thermal bleaching of the photogenerated colored isomers and hence the switch ability pattern of the photochromic material. The effect of molecular structure computed by DFT in gas-phase and solvents onCspiro-Obond length has been shown to correlate with photochromic properties. For this compound, DFT optimized geometry could be used to predict photochromism. Furthermore, in an attempt to predict the driving force for MC → SP, this work explores, for the first time, profitable exploitation of the calculated and visualized mapped electrostatic potential energy surfaces (ESP map). Interestingly, it seems that the electrostatic potential forces over the molecular fragments govern spirobond rupture/closure reactions. Thermodynamically, all-trans-colored isomer (CTT) is the most stable merocyanine-like form.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A New Approach for Studying Bond Rupture/Closure of a Spiro Benzopyran Photochromic Material: Reactivity Descriptors Derived from Frontier Orbitals and DFT Computed Electrostatic Potential Energy Surface Maps

Abdel‐Mottaleb

Ali

2016

International Journal of Photoenergy

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“…Heterocyclic spiropyrans of different series are potential substances which can possess photochromic properties as a result of reversible opening-closing reactions of the pyran ring under the effect of light (Bertleson, 1971;Durr, 1990;Minkin, 2004). This work extends our efforts in obtaining chelatofore functionalized spiropyrans (Bulanov et al, 2002(Bulanov et al, , 2003(Bulanov et al, , 2008(Bulanov et al, , 2009.…”

Section: Commentmentioning

confidence: 67%

“…The pyran ring is bent in such a way that the O2 0 atom of the oxaindane moiety is closer to the plane of the pyran ring. This conformation favours the conjugation between the lone pair of atom O2 0 and the antibonding orbital of the C2-O1 bond in the pyran ring, analogous to benzoxazinone (Bulanov et al, 2008) and other series (Minkin, 2004) of spiropyrans. In both compounds, strong intramolecular hydrogen bonds between neighbouring 7-OH and azomethine N atoms (O2-H2Á Á ÁN1) are observed; their geometric parameters are given in Tables 2 and 3.…”

Section: Figurementioning

confidence: 96%

Novel hydrazone derivatives of 7-hydroxy-3′,3′-dimethyl-3′H-spiro[chromene-2,1′-isobenzofuran]-8-carbaldehyde

et al. 2011

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The structures of new oxaindane spiropyrans derived from 7-hydroxy-3',3'-dimethyl-3'H-spiro[chromene-2,1'-isobenzofuran]-8-carbaldehyde (SP1), namely N-benzyl-2-[(7-hydroxy-3',3'-dimethyl-3'H-spiro[chromene-2,1'-isobenzofuran]-8-yl)methylidene]hydrazinecarbothioamide, C(27)H(25)N(3)O(3)S, (I), at 120 (2) K, and N'-[(7-hydroxy-3',3'-dimethyl-3'H-spiro[chromene-2,1'-isobenzofuran]-8-yl)methylidene]-4-methylbenzohydrazide acetone monosolvate, C(27)H(24)N(2)O(4)·C(3)H(6)O, (II), at 100 (2) K, are reported. The photochromically active C(spiro)-O bond length in (I) is close to that in the parent compound (SP1), and in (II) it is shorter. In (I), centrosymmetric pairs of molecules are bound by two equivalent N-H...S hydrogen bonds, forming an eight-membered ring with two donors and two acceptors.

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“…However, most of researches of photoreversible metal complexation with spiropyrans were performed in organic solvents but in purely aqueous environment because of hydrophobic characteristics of the dominant CF of spiropyrans at equiribrium . We previously reported on cross‐linked hydrophilic copolymers carrying spiropyran units, which showed transparent and photoreversible metal complexation in water .…”

Section: Introductionmentioning

confidence: 99%

Swelling–shrinking behavior of hydrated noncross‐linked copolymer films in response to photoreversible isomerizaton and metal complexation of spiropyran units of the copolymers

Suzuki

Kitsukawa

Hirata

et al. 2013

Polymers for Advanced Techs

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The copolymer of hydroxypropyl methacrylate (HPMA) and photochromic spiropyran methacrylate (SPMA) has been synthesized. The films of the copolymer (P(HPMA-SPMA)) in a hydrated state showed reversible swelling-shrinking behavior in response to photoreversible isomerization and metal complexation of SPMA units in spite of covalently noncross-linked copolymers. In addition, the protonated open form of the SPMA units of the copolymer was possibly stabilized thermodynamically by the HPMA units from ultraviolet-visible absorption measurement of the hydrated P (HPMA-SPMA) film. On the other hand, the difference in color of the hydrated films between P(HPMA-AABMA) and P (NIPMA-AABMA), which was a copolymer of N-isopropyl methacryl amide (NIPMA) and azobenzene methacrylate (AABMA) as a pH indicator, was suggestive of the interference of the proximal hydroxyl groups of the immobilized HPMA units with protonation of the AABMA units. The HPMA units of the copolymers also contributed to improvement of thermodynamic stability of the metal complexes with the SPMA units.

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Synthesis, IR, UV/vis-, 1H NMR and DFT study of chelatophore functionalized 1,3-benzoxazinone spiropyrans

Cited by 15 publications

References 17 publications

A New Approach for Studying Bond Rupture/Closure of a Spiro Benzopyran Photochromic Material: Reactivity Descriptors Derived from Frontier Orbitals and DFT Computed Electrostatic Potential Energy Surface Maps

A New Approach for Studying Bond Rupture/Closure of a Spiro Benzopyran Photochromic Material: Reactivity Descriptors Derived from Frontier Orbitals and DFT Computed Electrostatic Potential Energy Surface Maps

Novel hydrazone derivatives of 7-hydroxy-3′,3′-dimethyl-3′H-spiro[chromene-2,1′-isobenzofuran]-8-carbaldehyde

Swelling–shrinking behavior of hydrated noncross‐linked copolymer films in response to photoreversible isomerizaton and metal complexation of spiropyran units of the copolymers

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