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
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...
Saved in:
| Main Authors: | , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley
2016-01-01
|
| Series: | International Journal of Photoenergy |
| Online Access: | http://dx.doi.org/10.1155/2016/6765805 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1832567527721402368 |
|---|---|
| author | M. S. A. Abdel-Mottaleb Sarah N. Ali |
| author_facet | M. S. A. Abdel-Mottaleb Sarah N. Ali |
| author_sort | M. S. A. Abdel-Mottaleb |
| collection | DOAJ |
| description | 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 on Cspiro-O bond 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. |
| format | Article |
| id | doaj-art-886c7d7cc10f4ec7900b584d37385a4e |
| institution | Kabale University |
| issn | 1110-662X 1687-529X |
| language | English |
| publishDate | 2016-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | International Journal of Photoenergy |
| spelling | doaj-art-886c7d7cc10f4ec7900b584d37385a4e2025-02-03T01:01:13ZengWileyInternational Journal of Photoenergy1110-662X1687-529X2016-01-01201610.1155/2016/67658056765805A 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 MapsM. S. A. Abdel-Mottaleb0Sarah N. Ali1Nano-Photochemistry and Solarchemistry Labs, Department of Chemistry, Faculty of Science, Ain Shams University, Abbassia, Cairo 11566, EgyptNano-Photochemistry and Solarchemistry Labs, Department of Chemistry, Faculty of Science, Ain Shams University, Abbassia, Cairo 11566, EgyptThis 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 on Cspiro-O bond 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.http://dx.doi.org/10.1155/2016/6765805 |
| spellingShingle | M. S. A. Abdel-Mottaleb Sarah N. Ali 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 International Journal of Photoenergy |
| title | 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 |
| title_full | 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 |
| title_fullStr | 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 |
| title_full_unstemmed | 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 |
| title_short | 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 |
| title_sort | 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 |
| url | http://dx.doi.org/10.1155/2016/6765805 |
| work_keys_str_mv | AT msaabdelmottaleb anewapproachforstudyingbondruptureclosureofaspirobenzopyranphotochromicmaterialreactivitydescriptorsderivedfromfrontierorbitalsanddftcomputedelectrostaticpotentialenergysurfacemaps AT sarahnali anewapproachforstudyingbondruptureclosureofaspirobenzopyranphotochromicmaterialreactivitydescriptorsderivedfromfrontierorbitalsanddftcomputedelectrostaticpotentialenergysurfacemaps AT msaabdelmottaleb newapproachforstudyingbondruptureclosureofaspirobenzopyranphotochromicmaterialreactivitydescriptorsderivedfromfrontierorbitalsanddftcomputedelectrostaticpotentialenergysurfacemaps AT sarahnali newapproachforstudyingbondruptureclosureofaspirobenzopyranphotochromicmaterialreactivitydescriptorsderivedfromfrontierorbitalsanddftcomputedelectrostaticpotentialenergysurfacemaps |