Acoplanarity, Aromaticity, Chirality, and Helical Twisting Power of Chlorin e6 13(N)-Methylamide-15,17-dimethyl Ester Complexes: Effect of a Metal
The experimental and theoretical study of the influence of metal complexing on geometry, aromaticity, chirality, and the ability to twist the nematic phase by complexes based on modified natural chlorin e6 was carried out. The geometry optimization of the chlorin e6 13(N)-methylamide-15,17-dimethyl...
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MDPI AG
2023-01-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/11/1/24 |
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| author | Vladimir Burmistrov Viktor Aleksandriiskii Igor Novikov Alena Batrakova Dmitry Belykh Olga Startseva Oskar I. Koifman |
| author_facet | Vladimir Burmistrov Viktor Aleksandriiskii Igor Novikov Alena Batrakova Dmitry Belykh Olga Startseva Oskar I. Koifman |
| author_sort | Vladimir Burmistrov |
| collection | DOAJ |
| description | The experimental and theoretical study of the influence of metal complexing on geometry, aromaticity, chirality, and the ability to twist the nematic phase by complexes based on modified natural chlorin e6 was carried out. The geometry optimization of the chlorin e6 13(N)-methylamide-15,17-dimethyl ester (MADMECl) and its Zn, Cu, and Ni complexes by DFT (CAM-B3LYP/6–31 G(d,p) functional) method was performed. Based on these calculations, the acoplanarity degree of the macrocyclic ligand and the distortion energy of its dianion were estimated, which allowed the arrangement of the MADMECl complexes in the series Ni > Cu > Zn. Aromaticity was evaluated using the NICS criterion (nuclear independent chemical shift). An increase in the degree of aromaticity of the macrocycle upon complex formation was established. At the same time, the aromaticity of the inner conjugation contour corresponds to the same series as the acoplanarity, while the outer π-delocalization is characterized by the reverse sequence. An experimental evaluation of the electron circular dichroism of the Soret and the Q-bands, as well as the g-factor of dissymmetry, was carried out. The growth of these parameters with an increase in the degree of acoplanarity and aromaticity of the internal conjugation contour was determined. The induction of helical phases in mixtures of nematic liquid crystals (LCs) based on cyanobiphenyls and MADMECl macrocyclic metal complexes was studied by polarization microscopy, and the clearance temperatures and helix pitch of the mesophases were measured. A strong effect of the metal on the phase transition temperature and helical twisting power was established. |
| first_indexed | 2024-03-09T12:15:51Z |
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| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-09T12:15:51Z |
| publishDate | 2023-01-01 |
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| series | Inorganics |
| spelling | doaj.art-6e7283a9111f44179a3f362a339ea0be2023-11-30T22:47:14ZengMDPI AGInorganics2304-67402023-01-011112410.3390/inorganics11010024Acoplanarity, Aromaticity, Chirality, and Helical Twisting Power of Chlorin e6 13(N)-Methylamide-15,17-dimethyl Ester Complexes: Effect of a MetalVladimir Burmistrov0Viktor Aleksandriiskii1Igor Novikov2Alena Batrakova3Dmitry Belykh4Olga Startseva5Oskar I. Koifman6Research Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology, Sheremetev Av. 7, 153000 Ivanovo, RussiaResearch Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology, Sheremetev Av. 7, 153000 Ivanovo, RussiaResearch Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology, Sheremetev Av. 7, 153000 Ivanovo, RussiaResearch Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology, Sheremetev Av. 7, 153000 Ivanovo, RussiaResearch Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology, Sheremetev Av. 7, 153000 Ivanovo, RussiaResearch Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology, Sheremetev Av. 7, 153000 Ivanovo, RussiaResearch Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology, Sheremetev Av. 7, 153000 Ivanovo, RussiaThe experimental and theoretical study of the influence of metal complexing on geometry, aromaticity, chirality, and the ability to twist the nematic phase by complexes based on modified natural chlorin e6 was carried out. The geometry optimization of the chlorin e6 13(N)-methylamide-15,17-dimethyl ester (MADMECl) and its Zn, Cu, and Ni complexes by DFT (CAM-B3LYP/6–31 G(d,p) functional) method was performed. Based on these calculations, the acoplanarity degree of the macrocyclic ligand and the distortion energy of its dianion were estimated, which allowed the arrangement of the MADMECl complexes in the series Ni > Cu > Zn. Aromaticity was evaluated using the NICS criterion (nuclear independent chemical shift). An increase in the degree of aromaticity of the macrocycle upon complex formation was established. At the same time, the aromaticity of the inner conjugation contour corresponds to the same series as the acoplanarity, while the outer π-delocalization is characterized by the reverse sequence. An experimental evaluation of the electron circular dichroism of the Soret and the Q-bands, as well as the g-factor of dissymmetry, was carried out. The growth of these parameters with an increase in the degree of acoplanarity and aromaticity of the internal conjugation contour was determined. The induction of helical phases in mixtures of nematic liquid crystals (LCs) based on cyanobiphenyls and MADMECl macrocyclic metal complexes was studied by polarization microscopy, and the clearance temperatures and helix pitch of the mesophases were measured. A strong effect of the metal on the phase transition temperature and helical twisting power was established.https://www.mdpi.com/2304-6740/11/1/24macroheterocyclic metal complexesgeometryaromaticitychiralityinduction of helical phaseshelical twisting power |
| spellingShingle | Vladimir Burmistrov Viktor Aleksandriiskii Igor Novikov Alena Batrakova Dmitry Belykh Olga Startseva Oskar I. Koifman Acoplanarity, Aromaticity, Chirality, and Helical Twisting Power of Chlorin e6 13(N)-Methylamide-15,17-dimethyl Ester Complexes: Effect of a Metal Inorganics macroheterocyclic metal complexes geometry aromaticity chirality induction of helical phases helical twisting power |
| title | Acoplanarity, Aromaticity, Chirality, and Helical Twisting Power of Chlorin e6 13(N)-Methylamide-15,17-dimethyl Ester Complexes: Effect of a Metal |
| title_full | Acoplanarity, Aromaticity, Chirality, and Helical Twisting Power of Chlorin e6 13(N)-Methylamide-15,17-dimethyl Ester Complexes: Effect of a Metal |
| title_fullStr | Acoplanarity, Aromaticity, Chirality, and Helical Twisting Power of Chlorin e6 13(N)-Methylamide-15,17-dimethyl Ester Complexes: Effect of a Metal |
| title_full_unstemmed | Acoplanarity, Aromaticity, Chirality, and Helical Twisting Power of Chlorin e6 13(N)-Methylamide-15,17-dimethyl Ester Complexes: Effect of a Metal |
| title_short | Acoplanarity, Aromaticity, Chirality, and Helical Twisting Power of Chlorin e6 13(N)-Methylamide-15,17-dimethyl Ester Complexes: Effect of a Metal |
| title_sort | acoplanarity aromaticity chirality and helical twisting power of chlorin e6 13 n methylamide 15 17 dimethyl ester complexes effect of a metal |
| topic | macroheterocyclic metal complexes geometry aromaticity chirality induction of helical phases helical twisting power |
| url | https://www.mdpi.com/2304-6740/11/1/24 |
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