EXCHANGE REACTIONS OF DECANOATE LIGANDS OF ZIRCONIUM AND HAFNIUM PHTHALOCYANINES
The reactions of exchange of decanoate ligands in di(decanoato)phthalocyaninates ofzirconium and hafnium with substituted benzoic and cinnamic acids have been studied. The structure of the obtained complexes was confirmed by 1H NMR and their reactivity in reactions with dibenzoylmethane was determin...
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| Date: | 2024 |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2024
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oai:ojs2.1444248.nisspano.web.hosting-test.net:article-6252024-11-19T15:09:57Z EXCHANGE REACTIONS OF DECANOATE LIGANDS OF ZIRCONIUM AND HAFNIUM PHTHALOCYANINES Chernii, Viktor Fedosova, Natalia phthalocyanines, zirconium, hafnium, synthesis, arylate ligands, cinnamoylate ligands. The reactions of exchange of decanoate ligands in di(decanoato)phthalocyaninates ofzirconium and hafnium with substituted benzoic and cinnamic acids have been studied. The structure of the obtained complexes was confirmed by 1H NMR and their reactivity in reactions with dibenzoylmethane was determined. In the 1H NMR spectra of all the obtained complexes there are no proton signals of the starting decanoate ligands in the region of 1.1–0 ppm. Instead, the spectra contain signals of substituted benzoate or cinnamate ligands. For example, in the case of complexes with 4-substituted benzoic acids, the 1H NMR spectra show signals characteristic of para-substituted benzene nuclei of out-of-plane coordinated ligands (two doublets), which are in a stronger field relative to the original benzoic acids. The influence of di(arylato) and di(cinnamoylato) ligands on the UV-Vis spectra of the obtained compounds in various solvents has been studied. The effect of solvent polarity on absorption in the near-IR range is shown. The UV-Vis spectra of phthalocyanine complexes are characterized by B- (Soret) band in the region of 330–340 nm, Q-band in the region of 690 nm and its vibrational satellite in the region of 625 nm, which is typical for phthalocyaninates. The long-wave Q-band is the most sensitive to structural changes of the phthalocyanine molecule. It has been found that the replacement of decanoate ligands with arylate- or cinnamoylate ligands in zirconium and hafnium phthalocyaninates does not significantly affect the position of the Q-band in the UV-Vis spectra. However, the maximum of the Q-band depends on the relative polarity of the solvents: with its increase, a hypsochromic shift of the maximum is observed. The solvent-dependent change of the Q-band position is relatively small (~10 nm). The position of the B-band maximum is practically independent of the nature of the solvent, but in more polar solvents there is a tendency to increase the relative intensity of this band. V.I.Vernadsky Institute of General and Inorganic Chemistry 2024-01-26 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/625 10.33609/2708-129X.89.12.2023.77-87 Ukrainian Chemistry Journal; Vol. 89 No. 12 (2023): Ukrainian Chemistry Journal; 77-87 Украинский химический журнал; Том 89 № 12 (2023): Ukrainian Chemistry Journal; 77-87 Український хімічний журнал; Том 89 № 12 (2023): Ukrainian Chemistry Journal; 77-87 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/625/311 |
| institution |
Ukrainian Chemistry Journal |
| baseUrl_str |
|
| datestamp_date |
2024-11-19T15:09:57Z |
| collection |
OJS |
| language |
English |
| topic_facet |
phthalocyanines zirconium hafnium synthesis arylate ligands cinnamoylate ligands. |
| format |
Article |
| author |
Chernii, Viktor Fedosova, Natalia |
| spellingShingle |
Chernii, Viktor Fedosova, Natalia EXCHANGE REACTIONS OF DECANOATE LIGANDS OF ZIRCONIUM AND HAFNIUM PHTHALOCYANINES |
| author_facet |
Chernii, Viktor Fedosova, Natalia |
| author_sort |
Chernii, Viktor |
| title |
EXCHANGE REACTIONS OF DECANOATE LIGANDS OF ZIRCONIUM AND HAFNIUM PHTHALOCYANINES |
| title_short |
EXCHANGE REACTIONS OF DECANOATE LIGANDS OF ZIRCONIUM AND HAFNIUM PHTHALOCYANINES |
| title_full |
EXCHANGE REACTIONS OF DECANOATE LIGANDS OF ZIRCONIUM AND HAFNIUM PHTHALOCYANINES |
| title_fullStr |
EXCHANGE REACTIONS OF DECANOATE LIGANDS OF ZIRCONIUM AND HAFNIUM PHTHALOCYANINES |
| title_full_unstemmed |
EXCHANGE REACTIONS OF DECANOATE LIGANDS OF ZIRCONIUM AND HAFNIUM PHTHALOCYANINES |
| title_sort |
exchange reactions of decanoate ligands of zirconium and hafnium phthalocyanines |
| description |
The reactions of exchange of decanoate ligands in di(decanoato)phthalocyaninates ofzirconium and hafnium with substituted benzoic and cinnamic acids have been studied. The structure of the obtained complexes was confirmed by 1H NMR and their reactivity in reactions with dibenzoylmethane was determined. In the 1H NMR spectra of all the obtained complexes there are no proton signals of the starting decanoate ligands in the region of 1.1–0 ppm. Instead, the spectra contain signals of substituted benzoate or cinnamate ligands. For example, in the case of complexes with 4-substituted benzoic acids, the 1H NMR spectra show signals characteristic of para-substituted benzene nuclei of out-of-plane coordinated ligands (two doublets), which are in a stronger field relative to the original benzoic acids. The influence of di(arylato) and di(cinnamoylato) ligands on the UV-Vis spectra of the obtained compounds in various solvents has been studied. The effect of solvent polarity on absorption in the near-IR range is shown. The UV-Vis spectra of phthalocyanine complexes are characterized by B- (Soret) band in the region of 330–340 nm, Q-band in the region of 690 nm and its vibrational satellite in the region of 625 nm, which is typical for phthalocyaninates. The long-wave Q-band is the most sensitive to structural changes of the phthalocyanine molecule. It has been found that the replacement of decanoate ligands with arylate- or cinnamoylate ligands in zirconium and hafnium phthalocyaninates does not significantly affect the position of the Q-band in the UV-Vis spectra. However, the maximum of the Q-band depends on the relative polarity of the solvents: with its increase, a hypsochromic shift of the maximum is observed. The solvent-dependent change of the Q-band position is relatively small (~10 nm). The position of the B-band maximum is practically independent of the nature of the solvent, but in more polar solvents there is a tendency to increase the relative intensity of this band. |
| publisher |
V.I.Vernadsky Institute of General and Inorganic Chemistry |
| publishDate |
2024 |
| url |
https://ucj.org.ua/index.php/journal/article/view/625 |
| work_keys_str_mv |
AT cherniiviktor exchangereactionsofdecanoateligandsofzirconiumandhafniumphthalocyanines AT fedosovanatalia exchangereactionsofdecanoateligandsofzirconiumandhafniumphthalocyanines |
| first_indexed |
2025-09-24T17:43:54Z |
| last_indexed |
2025-09-24T17:43:54Z |
| _version_ |
1849658131094700032 |