{"title":"过渡金属配合物中希夫碱和吡啶衍生物混合配体的电子结构、电子能谱分析及吸收光谱分析","authors":"Ghouzala Boukehil, Mohamed Amine Zerizer, Sabri Mecheri, Bachir Zouchoune","doi":"10.1007/s11224-025-02465-y","DOIUrl":null,"url":null,"abstract":"<p>DFT calculations using BP86, PBE, and B3LYP functionals have been carried out on a series of complexes of the types [M(L1)(L2)]<sup>2+</sup>, [M(L2)<sub>2</sub>]<sup>2+</sup>, [M(L2)(L3)<sub>2</sub>]<sup>2+</sup>, and [M((L3)<sub>4</sub>]<sup>2+</sup> (M = Ni, Pd, Cu, Zn, and L1 = N-(4methoxybenzylidene) isonicotihydrazone bidentate Schiff base, L2 = 2,2′-bipyridine, and L3 = pyridine). A complete rationalization of bonding is provided of these kinds of complexes, where the predicted structures provide to the M(II) cations a perfect square planar geometry for Ni(II), Pd(II), and Cu(II) and a tetrahedral one for Zn(II). Large HOMO–LUMO gaps are calculated for all optimized structures of singlet spin state except for Cu(II) with a doublet spin state; suggesting a good kinetic stability. The low singlet spin state for Ni(II), Pd(II), and Zn(II) and the doublet spin state for Cu(II) complexes are characterized by BP86, PBE, and B3LYP functionals as ground states compared to those of high triplet and quartet spin ones, respectively. The TD-DFT theoretical study performed on the optimized geometries permitted us to predict the UV–Vis spectra and to pinpoint accurately the spectral positions and the nature of the different electronic transitions according to their molecular orbital localization; hence, the available experimental UV–Vis spectra are compared to our findings. The electronic spectra obtained in ethanol solvent show red shifts for complexed species due to the coordination of free ligands with metal cations characterized by HOMO → LUMO and HOMO-1 → LUMO electronic transitions.</p>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 4","pages":"1381 - 1395"},"PeriodicalIF":2.2000,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Electronic structures and EDA-NOCV and absorption spectra analysis of Schiff base and pyridine derivatives mixed ligands in transition metal complexes\",\"authors\":\"Ghouzala Boukehil, Mohamed Amine Zerizer, Sabri Mecheri, Bachir Zouchoune\",\"doi\":\"10.1007/s11224-025-02465-y\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>DFT calculations using BP86, PBE, and B3LYP functionals have been carried out on a series of complexes of the types [M(L1)(L2)]<sup>2+</sup>, [M(L2)<sub>2</sub>]<sup>2+</sup>, [M(L2)(L3)<sub>2</sub>]<sup>2+</sup>, and [M((L3)<sub>4</sub>]<sup>2+</sup> (M = Ni, Pd, Cu, Zn, and L1 = N-(4methoxybenzylidene) isonicotihydrazone bidentate Schiff base, L2 = 2,2′-bipyridine, and L3 = pyridine). A complete rationalization of bonding is provided of these kinds of complexes, where the predicted structures provide to the M(II) cations a perfect square planar geometry for Ni(II), Pd(II), and Cu(II) and a tetrahedral one for Zn(II). Large HOMO–LUMO gaps are calculated for all optimized structures of singlet spin state except for Cu(II) with a doublet spin state; suggesting a good kinetic stability. The low singlet spin state for Ni(II), Pd(II), and Zn(II) and the doublet spin state for Cu(II) complexes are characterized by BP86, PBE, and B3LYP functionals as ground states compared to those of high triplet and quartet spin ones, respectively. The TD-DFT theoretical study performed on the optimized geometries permitted us to predict the UV–Vis spectra and to pinpoint accurately the spectral positions and the nature of the different electronic transitions according to their molecular orbital localization; hence, the available experimental UV–Vis spectra are compared to our findings. The electronic spectra obtained in ethanol solvent show red shifts for complexed species due to the coordination of free ligands with metal cations characterized by HOMO → LUMO and HOMO-1 → LUMO electronic transitions.</p>\",\"PeriodicalId\":780,\"journal\":{\"name\":\"Structural Chemistry\",\"volume\":\"36 4\",\"pages\":\"1381 - 1395\"},\"PeriodicalIF\":2.2000,\"publicationDate\":\"2025-01-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Structural Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11224-025-02465-y\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11224-025-02465-y","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Electronic structures and EDA-NOCV and absorption spectra analysis of Schiff base and pyridine derivatives mixed ligands in transition metal complexes
DFT calculations using BP86, PBE, and B3LYP functionals have been carried out on a series of complexes of the types [M(L1)(L2)]2+, [M(L2)2]2+, [M(L2)(L3)2]2+, and [M((L3)4]2+ (M = Ni, Pd, Cu, Zn, and L1 = N-(4methoxybenzylidene) isonicotihydrazone bidentate Schiff base, L2 = 2,2′-bipyridine, and L3 = pyridine). A complete rationalization of bonding is provided of these kinds of complexes, where the predicted structures provide to the M(II) cations a perfect square planar geometry for Ni(II), Pd(II), and Cu(II) and a tetrahedral one for Zn(II). Large HOMO–LUMO gaps are calculated for all optimized structures of singlet spin state except for Cu(II) with a doublet spin state; suggesting a good kinetic stability. The low singlet spin state for Ni(II), Pd(II), and Zn(II) and the doublet spin state for Cu(II) complexes are characterized by BP86, PBE, and B3LYP functionals as ground states compared to those of high triplet and quartet spin ones, respectively. The TD-DFT theoretical study performed on the optimized geometries permitted us to predict the UV–Vis spectra and to pinpoint accurately the spectral positions and the nature of the different electronic transitions according to their molecular orbital localization; hence, the available experimental UV–Vis spectra are compared to our findings. The electronic spectra obtained in ethanol solvent show red shifts for complexed species due to the coordination of free ligands with metal cations characterized by HOMO → LUMO and HOMO-1 → LUMO electronic transitions.
期刊介绍:
Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry.
We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.