Zn(ii) complexes with thiazolyl-hydrazones: structure, intermolecular interactions, photophysical properties, computational study and anticancer activity
Само за регистроване кориснике
2022
Аутори
Araškov, Jovana B.Višnjevac, Aleksandar
Popović, Jasminka
Blagojević, Vladimir
Fernandes, Henrique S.
Sousa, Sérgio F.
Novaković, Irena
Padrón, José M.
Holló, Berta Barta
Monge, Miguel
Rodríguez-Castillo, María
López-De-Luzuriaga, José M.
Filipović, Nenad
Todorović, Tamara
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
Earth-abundant, cheap and non-toxic zinc-based coordination compounds are drawing research attention as promising candidates for various applications, such as photoluminescent materials and anticancer agents. In this paper we report six zinc complexes (1-3-NO3 and 1-3-Cl) with pyridyl-based thiazolyl-hydrazone ligands, which differ in the nature of substituents at the ligands' periphery, anion type, and geometry around the metal ion. The complexes were characterized by single-crystal and powder X-ray diffraction analysis, as well as IR and NMR spectroscopy. The symmetrical complexes 2-Cl and 3-Cl, where zinc atoms are located at a two-fold axis, do not exhibit photophysical properties, unlike their asymmetrical analogs 2-NO3 and 3-NO3 with the same complex cation. Asymmetrical pentacoordinated 1-Cl and hexacoordinated 1-NO3 complexes exhibit photophysical properties. An admixture of allowed intra-ligand (1IL) and chloro (X)-to-ligand charge-transfer (1XLCT) electronic transitions is re...sponsible for the fluorescence of the 1-Cl complex. The origin of the emission of the 1-NO3 complex is ascribed to an admixture of 3IL and ligand-to-ligand charge-transfer (3LLCT) forbidden electronic transitions, while for 3-NO3 most electronic excitations are of LLCT character. The thermal stability of the complexes is in accord with the strength of respective intermolecular interactions. The antiproliferative activity of the complexes was in the nanomolar range on some of the investigated cancer cell lines. Contrary to the increase of antiproliferative activity of the complexes in comparison to the free ligands in cancer cell lines, an acute toxicity determined in the brine shrimp assay follows the opposite trend. The overall results suggest that Zn(ii) thiazoyl-hydrazone complexes have considerable potential as multifunctional materials.
Кључне речи:
Zn(II) complexes / thiazolyl-hydrazones / anticancer activityИзвор:
CrystEngComm, 2022, 24, 29, 5194-5214Издавач:
- Royal Society of Chemistry
Финансирање / пројекти:
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200116 (Универзитет у Београду, Пољопривредни факултет) (RS-MESTD-inst-2020-200116)
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200168 (Универзитет у Београду, Хемијски факултет) (RS-MESTD-inst-2020-200168)
- The Spanish Government (PGC2018-094503-B-C22, MCIU/AEI/FEDER, UE)
- The Canary Islands Government (ProID2020010101, ACIISI/FEDER, UE)
- J. M. L. L. Grant PID2019-104379RB-C22 funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe”.
- The Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding UIDP/04378/2020
- The Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding and UIDB/04378/2020.
- FCT by funding 2020.01423.CEECIND/CP1596/CT0003
- The FCT and FEDER under project 01/SAICT/ 2016 number 022153
- CPCA/A00/7140/2020
- CPCA/A00/7145/2020
DOI: 10.1039/d2ce00443g
ISSN: 1466-8033
WoS: 000813632500001
Scopus: 2-s2.0-85132527018
Институција/група
IHTMTY - JOUR AU - Araškov, Jovana B. AU - Višnjevac, Aleksandar AU - Popović, Jasminka AU - Blagojević, Vladimir AU - Fernandes, Henrique S. AU - Sousa, Sérgio F. AU - Novaković, Irena AU - Padrón, José M. AU - Holló, Berta Barta AU - Monge, Miguel AU - Rodríguez-Castillo, María AU - López-De-Luzuriaga, José M. AU - Filipović, Nenad AU - Todorović, Tamara PY - 2022 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/5431 AB - Earth-abundant, cheap and non-toxic zinc-based coordination compounds are drawing research attention as promising candidates for various applications, such as photoluminescent materials and anticancer agents. In this paper we report six zinc complexes (1-3-NO3 and 1-3-Cl) with pyridyl-based thiazolyl-hydrazone ligands, which differ in the nature of substituents at the ligands' periphery, anion type, and geometry around the metal ion. The complexes were characterized by single-crystal and powder X-ray diffraction analysis, as well as IR and NMR spectroscopy. The symmetrical complexes 2-Cl and 3-Cl, where zinc atoms are located at a two-fold axis, do not exhibit photophysical properties, unlike their asymmetrical analogs 2-NO3 and 3-NO3 with the same complex cation. Asymmetrical pentacoordinated 1-Cl and hexacoordinated 1-NO3 complexes exhibit photophysical properties. An admixture of allowed intra-ligand (1IL) and chloro (X)-to-ligand charge-transfer (1XLCT) electronic transitions is responsible for the fluorescence of the 1-Cl complex. The origin of the emission of the 1-NO3 complex is ascribed to an admixture of 3IL and ligand-to-ligand charge-transfer (3LLCT) forbidden electronic transitions, while for 3-NO3 most electronic excitations are of LLCT character. The thermal stability of the complexes is in accord with the strength of respective intermolecular interactions. The antiproliferative activity of the complexes was in the nanomolar range on some of the investigated cancer cell lines. Contrary to the increase of antiproliferative activity of the complexes in comparison to the free ligands in cancer cell lines, an acute toxicity determined in the brine shrimp assay follows the opposite trend. The overall results suggest that Zn(ii) thiazoyl-hydrazone complexes have considerable potential as multifunctional materials. PB - Royal Society of Chemistry T2 - CrystEngComm T1 - Zn(ii) complexes with thiazolyl-hydrazones: structure, intermolecular interactions, photophysical properties, computational study and anticancer activity VL - 24 IS - 29 SP - 5194 EP - 5214 DO - 10.1039/d2ce00443g ER -
@article{ author = "Araškov, Jovana B. and Višnjevac, Aleksandar and Popović, Jasminka and Blagojević, Vladimir and Fernandes, Henrique S. and Sousa, Sérgio F. and Novaković, Irena and Padrón, José M. and Holló, Berta Barta and Monge, Miguel and Rodríguez-Castillo, María and López-De-Luzuriaga, José M. and Filipović, Nenad and Todorović, Tamara", year = "2022", abstract = "Earth-abundant, cheap and non-toxic zinc-based coordination compounds are drawing research attention as promising candidates for various applications, such as photoluminescent materials and anticancer agents. In this paper we report six zinc complexes (1-3-NO3 and 1-3-Cl) with pyridyl-based thiazolyl-hydrazone ligands, which differ in the nature of substituents at the ligands' periphery, anion type, and geometry around the metal ion. The complexes were characterized by single-crystal and powder X-ray diffraction analysis, as well as IR and NMR spectroscopy. The symmetrical complexes 2-Cl and 3-Cl, where zinc atoms are located at a two-fold axis, do not exhibit photophysical properties, unlike their asymmetrical analogs 2-NO3 and 3-NO3 with the same complex cation. Asymmetrical pentacoordinated 1-Cl and hexacoordinated 1-NO3 complexes exhibit photophysical properties. An admixture of allowed intra-ligand (1IL) and chloro (X)-to-ligand charge-transfer (1XLCT) electronic transitions is responsible for the fluorescence of the 1-Cl complex. The origin of the emission of the 1-NO3 complex is ascribed to an admixture of 3IL and ligand-to-ligand charge-transfer (3LLCT) forbidden electronic transitions, while for 3-NO3 most electronic excitations are of LLCT character. The thermal stability of the complexes is in accord with the strength of respective intermolecular interactions. The antiproliferative activity of the complexes was in the nanomolar range on some of the investigated cancer cell lines. Contrary to the increase of antiproliferative activity of the complexes in comparison to the free ligands in cancer cell lines, an acute toxicity determined in the brine shrimp assay follows the opposite trend. The overall results suggest that Zn(ii) thiazoyl-hydrazone complexes have considerable potential as multifunctional materials.", publisher = "Royal Society of Chemistry", journal = "CrystEngComm", title = "Zn(ii) complexes with thiazolyl-hydrazones: structure, intermolecular interactions, photophysical properties, computational study and anticancer activity", volume = "24", number = "29", pages = "5194-5214", doi = "10.1039/d2ce00443g" }
Araškov, J. B., Višnjevac, A., Popović, J., Blagojević, V., Fernandes, H. S., Sousa, S. F., Novaković, I., Padrón, J. M., Holló, B. B., Monge, M., Rodríguez-Castillo, M., López-De-Luzuriaga, J. M., Filipović, N.,& Todorović, T.. (2022). Zn(ii) complexes with thiazolyl-hydrazones: structure, intermolecular interactions, photophysical properties, computational study and anticancer activity. in CrystEngComm Royal Society of Chemistry., 24(29), 5194-5214. https://doi.org/10.1039/d2ce00443g
Araškov JB, Višnjevac A, Popović J, Blagojević V, Fernandes HS, Sousa SF, Novaković I, Padrón JM, Holló BB, Monge M, Rodríguez-Castillo M, López-De-Luzuriaga JM, Filipović N, Todorović T. Zn(ii) complexes with thiazolyl-hydrazones: structure, intermolecular interactions, photophysical properties, computational study and anticancer activity. in CrystEngComm. 2022;24(29):5194-5214. doi:10.1039/d2ce00443g .
Araškov, Jovana B., Višnjevac, Aleksandar, Popović, Jasminka, Blagojević, Vladimir, Fernandes, Henrique S., Sousa, Sérgio F., Novaković, Irena, Padrón, José M., Holló, Berta Barta, Monge, Miguel, Rodríguez-Castillo, María, López-De-Luzuriaga, José M., Filipović, Nenad, Todorović, Tamara, "Zn(ii) complexes with thiazolyl-hydrazones: structure, intermolecular interactions, photophysical properties, computational study and anticancer activity" in CrystEngComm, 24, no. 29 (2022):5194-5214, https://doi.org/10.1039/d2ce00443g . .