%0 Journal Article %1 gong2002tms %A Gong, Xue Dong %A Xiao, He Ming %A Tian, He %D 2002 %J Journal of Molecular Structure: THEOCHEM %K diplom festkörper %N 1-3 %P 93 - 100 %R 10.1016/S0166-1280(02)00302-0 %T A density functional theory study on the structure and properties of the tert-butyl substituted phthalocyanines %U http://www.sciencedirect.com/science/article/pii/S0166128002003020 %V 593 %X The geometries of the four isomers of mono tert-butyl substituted phthalocyanine, I, II, III, and IV, have been optimized at the B3LYP/3-21G level of density functional theory. Single-point energy calculations have been carried out at the B3LYP/6-311G*//B3LYP/3-21G level. According to the computational results, the energies of the four isomers increase in the order of IV<II<III<I. The enthalpies of formation derived from an isodesmic reaction are 1307.83, 1286.87, 1307.40, and 1285.88 kJ/mol for I, II, III, and IV, respectively. The isomer IV has the lowest energy, which implies that the substitution at the peripheral position of the isoindole with the inner hydrogen atom is the most favorable. Substitution mainly affects the geometrical parameters of the isoindole unit that the substituent attaches and has a small influence on the electronic structures. Normal mode vibrational analysis has been performed, and the standard thermodynamic functions of various isomers have been evaluated. The UV-Vis spectra of the tert-butyl substituted Pcs have been calculated using the ZINDO method. The obtained spectra have two strong Q absorption bands around 700 and 750 nm and one very strong B band around 290 nm. The calculated results have been compared with those of Pc and the trimethylsilyl Pcs to evaluate the effect of the tert-butyl substitution.

@article{gong2002tms, abstract = {The geometries of the four isomers of mono tert-butyl substituted phthalocyanine, I, II, III, and IV, have been optimized at the B3LYP/3-21G level of density functional theory. Single-point energy calculations have been carried out at the B3LYP/6-311G*//B3LYP/3-21G level. According to the computational results, the energies of the four isomers increase in the order of IV<II<III<I. The enthalpies of formation derived from an isodesmic reaction are 1307.83, 1286.87, 1307.40, and 1285.88 kJ/mol for I, II, III, and IV, respectively. The isomer IV has the lowest energy, which implies that the substitution at the peripheral position of the isoindole with the inner hydrogen atom is the most favorable. Substitution mainly affects the geometrical parameters of the isoindole unit that the substituent attaches and has a small influence on the electronic structures. Normal mode vibrational analysis has been performed, and the standard thermodynamic functions of various isomers have been evaluated. The UV-Vis spectra of the tert-butyl substituted Pcs have been calculated using the ZINDO method. The obtained spectra have two strong Q absorption bands around 700 and 750 nm and one very strong B band around 290 nm. The calculated results have been compared with those of Pc and the trimethylsilyl Pcs to evaluate the effect of the tert-butyl substitution.}, added-at = {2011-06-24T10:34:41.000+0200}, author = {Gong, Xue Dong and Xiao, He Ming and Tian, He}, biburl = {https://www.bibsonomy.org/bibtex/2f035481106968ac2471207ceaa775699/bkoch}, description = {ScienceDirect - Journal of Molecular Structure: THEOCHEM : A density functional theory study on the structure and properties of the tert-butyl substituted phthalocyanines}, doi = {10.1016/S0166-1280(02)00302-0}, interhash = {31e085d3fd9e6accecd7f55695431910}, intrahash = {f035481106968ac2471207ceaa775699}, issn = {0166-1280}, journal = {Journal of Molecular Structure: THEOCHEM}, keywords = {diplom festkörper}, number = {1-3}, pages = {93 - 100}, timestamp = {2011-06-24T10:34:41.000+0200}, title = {A density functional theory study on the structure and properties of the tert-butyl substituted phthalocyanines}, url = {http://www.sciencedirect.com/science/article/pii/S0166128002003020}, volume = 593, year = 2002 }