Structural Variety, Luminescent Properties, and DFT Calculations of 2-Naphthaldehyde Thiosemicarbazone and Its Complexes with Zinc(II) and Cadmium(II).
4 affiliations
- 1Department of Inorganic Chemistry, Faculty of Pharmacy, University of Santiago de Compostela, 15782Santiago de Compostela, Spain.
- 2Departamento de Química Inorgánica, Facultade de Química, Universidade de Santiago de Compostela, 15782Santiago de Compostela, Spain.
- 3Institute of Materials (iMATUS), Universidade de Santiago de Compostela, 15782Santiago de Compostela, Spain.
- 4Departament de Química, Universitat de les Illes Balears, Crta e Valldemossa km 7.5, 07122Palma de Mallorca (Baleares), Spain.
Abstract
A 2-naphthyl functionalized thiosemicarbazone has been synthesized in high yield by means of a Schiff base condensation reaction. The 2-(naphthalen-2-ylmethylene)hydrazinecarbothioamide (Hnatsc, 1) reacts with zinc(II) and cadmium(II) chlorides and acetates to obtain neutral complexes of formulae: [ZnCl2(Hnatsc)2]·H2O (2·H2O), [Zn(natsc)2]·3H2O (3·3H2O), [Zn(natsc)2(Hnatsc)2]·3H2O (4·3H2O), [Zn(OAc)(natsc)(Hnatsc)]·2H2O (5·2H2O), [CdCl2(Hnatsc)2] (6), [Cd(natsc)2] (7), and [Cd(OAc)(natsc)(MeOH)] (8), in which the thiosemicarbazone functions as a monodentate thione ligand or as a deprotonated bidentate chelating ligand coordinating to the metal ions via the imine nitrogen and thiolate sulfur atoms. The characterization of all compounds was through a combination of analytical techniques, including elemental analysis, nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and electrospray ionization (ESI) mass spectrometry. The molecular and crystal structures of Hnatsc and complexes 2 and 6 were determined by means of single-crystal X-ray diffraction. Furthermore, a fluorescence study was conducted on the thiosemicarbazone and the complexes. A density functional theory (DFT) study using MEP, QTAIM, and NCIplot analyzed the supramolecular architecture, revealing that metal coordination significantly strengthens hydrogen-bonded synthons. Furthermore, TD-DFT calculations provided insight into the photophysical properties, confirming the ligand-centered nature of the electronic transitions and identifying high internal conversion rates as the primary quenching mechanism in the zinc complex 2.
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BibTeX
@article{castineiras2026structural,
title = {{Structural Variety, Luminescent Properties, and DFT Calculations of 2-Naphthaldehyde Thiosemicarbazone and Its Complexes with Zinc(II) and Cadmium(II).}},
author = {Alfonso Castiñeiras and Isabel García-Santos and Lorenzo Seijo and Julio Corredoira-Vázquez and Sergi Burguera and Antonio Frontera},
journal = {Inorganic chemistry},
year = {2026},
month = sep,
doi = {10.1021/acs.inorgchem.6c02677},
url = {https://europepmc.org/article/MED/42916495},
note = {CC BY},
}
RIS
TY - JOUR
TI - Structural Variety, Luminescent Properties, and DFT Calculations of 2-Naphthaldehyde Thiosemicarbazone and Its Complexes with Zinc(II) and Cadmium(II).
AU - Alfonso Castiñeiras
AU - Isabel García-Santos
AU - Lorenzo Seijo
AU - Julio Corredoira-Vázquez
AU - Sergi Burguera
AU - Antonio Frontera
PY - 2026
DA - 2026/09/01
JO - Inorganic chemistry
DO - 10.1021/acs.inorgchem.6c02677
UR - https://europepmc.org/article/MED/42916495
AB - A 2-naphthyl functionalized thiosemicarbazone has been synthesized in high yield by means of a Schiff base condensation reaction. The 2-(naphthalen-2-ylmethylene)hydrazinecarbothioamide (Hnatsc, 1) reacts with zinc(II) and cadmium(II) chlorides and acetates to obtain neutral complexes of formulae: [ZnCl2(Hnatsc)2]·H2O (2·H2O), [Zn(natsc)2]·3H2O (3·3H2O), [Zn(natsc)2(Hnatsc)2]·3H2O (4·3H2O), [Zn(OAc)(natsc)(Hnatsc)]·2H2O (5·2H2O), [CdCl2(Hnatsc)2] (6), [Cd(natsc)2] (7), and [Cd(OAc)(natsc)(MeOH)] (8), in which the thiosemicarbazone functions as a monodentate thione ligand or as a deprotonated bidentate chelating ligand coordinating to the metal ions via the imine nitrogen and thiolate sulfur atoms. The characterization of all compounds was through a combination of analytical techniques, including elemental analysis, nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and electrospray ionization (ESI) mass spectrometry. The molecular and crystal structures of Hnatsc and complexes 2 and 6 were determined by means of single-crystal X-ray diffraction. Furthermore, a fluorescence study was conducted on the thiosemicarbazone and the complexes. A density functional theory (DFT) study using MEP, QTAIM, and NCIplot analyzed the supramolecular architecture, revealing that metal coordination significantly strengthens hydrogen-bonded synthons. Furthermore, TD-DFT calculations provided insight into the photophysical properties, confirming the ligand-centered nature of the electronic transitions and identifying high internal conversion rates as the primary quenching mechanism in the zinc complex 2.
SN - 0020-1669
SN - 1520-510X
ER -