THE STUDY OF LIGAND EXCHANGE REACTIONS IN THE MIXED-LIGAND HAFNIUM PHTHALO-CYANINE COMPLEX BY 1H NMR SPECTROSCOPY
The reactivity of a mixed-ligand alkylamino-β-ketoenolato decanoatophthalocyaninate of hafnium was investigated by 1H NMR spectroscopy via substitution of axial ligands in reactions with para-isopropoxybenzoic acid and dibenzoylmethane. The initial complex PcHf(C₉H₁₉COO)L was shown to exhibit high r...
Saved in:
| Date: | 2026 |
|---|---|
| Main Authors: | , , , |
| Format: | Article |
| Language: | English |
| Published: |
V.I.Vernadsky Institute of General and Inorganic Chemistry
2026
|
| Online Access: | https://ucj.org.ua/index.php/journal/article/view/771 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Journal Title: | Ukrainian Chemistry Journal |
Institution
Ukrainian Chemistry Journal| _version_ | 1864036377028460544 |
|---|---|
| author | Tretyakova, Iryna Fedosova, Natalia Dovbiy, Yan Chernii, Viktor |
| author_facet | Tretyakova, Iryna Fedosova, Natalia Dovbiy, Yan Chernii, Viktor |
| author_sort | Tretyakova, Iryna |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-05-01T10:54:33Z |
| description | The reactivity of a mixed-ligand alkylamino-β-ketoenolato decanoatophthalocyaninate of hafnium was investigated by 1H NMR spectroscopy via substitution of axial ligands in reactions with para-isopropoxybenzoic acid and dibenzoylmethane. The initial complex PcHf(C₉H₁₉COO)L was shown to exhibit high reactivity. It was established that the presence of different axial ligands enables their selective or complete substitution depending on the nature of the reagent. In the reaction with  para-isopropoxybenzoic acid, only the decanoate ligand is replaced, leading to the formation of a new mixed-ligand complex  PcHf(C₁₀H₁₁O₃)L. The 1H NMR spectrum of the obtained complex displays signals of the phthalocyanine macrocycle protons (9.5–8.1 ppm) and the para-substituted benzoate fragment (7.5–7.4 ppm). Signals corresponding to the alkylamino-β-ketoenol ligand are observed in the region 7.2–5.5 ppm, as well as in the aliphatic region. The absence of signals corresponding to the decanoate chain protons (0.0–0.5 ppm) and the appearance of signals of the isopropyl methyl protons (2.27 ppm) confirm the completion of the ligand exchange reaction. In contrast, the reaction of PcHf(C₉H₁₉COO)L with dibenzoylmethane results in complete substitution of both axial ligands (decanoate and alkylamino-β-ketoenolate), yielding bis(dibenzoylmethanato)hafnium phthalocyaninate. The 1H NMR spectrum of the product shows no signals of either decanoate or alkylamino-β-ketoenolate protons and matches the previously reported spectrum of PcHf(dbm)₂. A stability series of chelate rings in the coordination sphere of hafnium phthalocyaninates was established. The strength of ligand binding to the central metal atom increases in the following order: aliphatic carboxylate < aromatic carboxylate < alkylamino-β-ketoenolate < β-diketonate.  The obtained results expand the possibilities for the targeted synthesis of out-of-plane coordinated phthalocyanine complexes, enabling the tuning of their physicochemical properties (such as solubility and spectral characteristics) for potential applications in photodynamic therapy, organic semiconductors, and sensors. |
| doi_str_mv | 10.33609/2708-129X.92.3.2026.18-26 |
| first_indexed | 2026-05-02T01:00:17Z |
| format | Article |
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-771 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-05-02T01:00:17Z |
| publishDate | 2026 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-7712026-05-01T10:54:33Z THE STUDY OF LIGAND EXCHANGE REACTIONS IN THE MIXED-LIGAND HAFNIUM PHTHALO-CYANINE COMPLEX BY 1H NMR SPECTROSCOPY Tretyakova, Iryna Fedosova, Natalia Dovbiy, Yan Chernii, Viktor phthalocyanine, hafnium, ligand exchange, 1H NMR spectroscopy, mixed ligand complexes. The reactivity of a mixed-ligand alkylamino-β-ketoenolato decanoatophthalocyaninate of hafnium was investigated by 1H NMR spectroscopy via substitution of axial ligands in reactions with para-isopropoxybenzoic acid and dibenzoylmethane. The initial complex PcHf(C₉H₁₉COO)L was shown to exhibit high reactivity. It was established that the presence of different axial ligands enables their selective or complete substitution depending on the nature of the reagent. In the reaction with  para-isopropoxybenzoic acid, only the decanoate ligand is replaced, leading to the formation of a new mixed-ligand complex  PcHf(C₁₀H₁₁O₃)L. The 1H NMR spectrum of the obtained complex displays signals of the phthalocyanine macrocycle protons (9.5–8.1 ppm) and the para-substituted benzoate fragment (7.5–7.4 ppm). Signals corresponding to the alkylamino-β-ketoenol ligand are observed in the region 7.2–5.5 ppm, as well as in the aliphatic region. The absence of signals corresponding to the decanoate chain protons (0.0–0.5 ppm) and the appearance of signals of the isopropyl methyl protons (2.27 ppm) confirm the completion of the ligand exchange reaction. In contrast, the reaction of PcHf(C₉H₁₉COO)L with dibenzoylmethane results in complete substitution of both axial ligands (decanoate and alkylamino-β-ketoenolate), yielding bis(dibenzoylmethanato)hafnium phthalocyaninate. The 1H NMR spectrum of the product shows no signals of either decanoate or alkylamino-β-ketoenolate protons and matches the previously reported spectrum of PcHf(dbm)₂. A stability series of chelate rings in the coordination sphere of hafnium phthalocyaninates was established. The strength of ligand binding to the central metal atom increases in the following order: aliphatic carboxylate < aromatic carboxylate < alkylamino-β-ketoenolate < β-diketonate.  The obtained results expand the possibilities for the targeted synthesis of out-of-plane coordinated phthalocyanine complexes, enabling the tuning of their physicochemical properties (such as solubility and spectral characteristics) for potential applications in photodynamic therapy, organic semiconductors, and sensors. V.I.Vernadsky Institute of General and Inorganic Chemistry 2026-04-30 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/771 10.33609/2708-129X.92.3.2026.18-26 Ukrainian Chemistry Journal; Vol. 92 No. 3 (2026): Ukrainian Chemistry Journal; 18-26 Украинский химический журнал; Том 92 № 3 (2026): Ukrainian Chemistry Journal; 18-26 Український хімічний журнал; Том 92 № 3 (2026): Ukrainian Chemistry Journal; 18-26 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/771/404 |
| spellingShingle | Tretyakova, Iryna Fedosova, Natalia Dovbiy, Yan Chernii, Viktor THE STUDY OF LIGAND EXCHANGE REACTIONS IN THE MIXED-LIGAND HAFNIUM PHTHALO-CYANINE COMPLEX BY 1H NMR SPECTROSCOPY |
| title | THE STUDY OF LIGAND EXCHANGE REACTIONS IN THE MIXED-LIGAND HAFNIUM PHTHALO-CYANINE COMPLEX BY 1H NMR SPECTROSCOPY |
| title_full | THE STUDY OF LIGAND EXCHANGE REACTIONS IN THE MIXED-LIGAND HAFNIUM PHTHALO-CYANINE COMPLEX BY 1H NMR SPECTROSCOPY |
| title_fullStr | THE STUDY OF LIGAND EXCHANGE REACTIONS IN THE MIXED-LIGAND HAFNIUM PHTHALO-CYANINE COMPLEX BY 1H NMR SPECTROSCOPY |
| title_full_unstemmed | THE STUDY OF LIGAND EXCHANGE REACTIONS IN THE MIXED-LIGAND HAFNIUM PHTHALO-CYANINE COMPLEX BY 1H NMR SPECTROSCOPY |
| title_short | THE STUDY OF LIGAND EXCHANGE REACTIONS IN THE MIXED-LIGAND HAFNIUM PHTHALO-CYANINE COMPLEX BY 1H NMR SPECTROSCOPY |
| title_sort | study of ligand exchange reactions in the mixed-ligand hafnium phthalo-cyanine complex by 1h nmr spectroscopy |
| topic_facet | phthalocyanine hafnium ligand exchange 1H NMR spectroscopy mixed ligand complexes. |
| url | https://ucj.org.ua/index.php/journal/article/view/771 |
| work_keys_str_mv | AT tretyakovairyna thestudyofligandexchangereactionsinthemixedligandhafniumphthalocyaninecomplexby1hnmrspectroscopy AT fedosovanatalia thestudyofligandexchangereactionsinthemixedligandhafniumphthalocyaninecomplexby1hnmrspectroscopy AT dovbiyyan thestudyofligandexchangereactionsinthemixedligandhafniumphthalocyaninecomplexby1hnmrspectroscopy AT cherniiviktor thestudyofligandexchangereactionsinthemixedligandhafniumphthalocyaninecomplexby1hnmrspectroscopy AT tretyakovairyna studyofligandexchangereactionsinthemixedligandhafniumphthalocyaninecomplexby1hnmrspectroscopy AT fedosovanatalia studyofligandexchangereactionsinthemixedligandhafniumphthalocyaninecomplexby1hnmrspectroscopy AT dovbiyyan studyofligandexchangereactionsinthemixedligandhafniumphthalocyaninecomplexby1hnmrspectroscopy AT cherniiviktor studyofligandexchangereactionsinthemixedligandhafniumphthalocyaninecomplexby1hnmrspectroscopy |