Copper(II) chelates derived from an N,N,O-tridentate 2-pyridinecarboxaldehyde-N4-phenylsemicarbazone: Synthesis, spectral aspects, crystal structure, FMO and NBO analysis

被引：8

作者：

Sithambaresan, M. ^{[1
,2
]}

Kurup, M. R. Prathapachandra ^{[1
]}

Serdaroglu, Goncagul ^{[3
]}

Kaya, Savas ^{[4
]}

机构：

[1] Cochin Univ Sci & Technol, Dept Appl Chem, Kochi 682022, Kerala, India

[2] Eastern Univ, Fac Sci, Dept Chem, Chenkalady, Sri Lanka

[3] Sivas Cumhuriyet Univ, Math & Sci Edu, TR-58140 Sivas, Turkiye

[4] Sivas Cumhuriyet Univ, Hlth Serv Vocat Sch, Dept Pharm, TR-58140 Sivas, Turkiye

来源：

JOURNAL OF MOLECULAR STRUCTURE | 2023年 / 1277卷

关键词：

2-Pyridinecarboxaldehyde; Semicarbazone; Copper(II) chelate; EPR spectrum; Quantum chemical parameters; NBO analysis; MOLECULAR-ORBITAL METHODS; COMPLEXES; SALICYLALDEHYDE; SEMICARBAZONE; HARDNESS; THIOSEMICARBAZONES; LIGANDS; CU(II);

D O I：

10.1016/j.molstruc.2022.134866

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Seven novel Cu(II) complexes [Cu(HPySc)Cl2] (1), [Cu2(PySc)2(NO3)2] middotH2O (2), [Cu(HPySc)(SO4)] middot1/2H2O (3), [Cu2(PySc)2(OAc)2] middotCH3OH (4), [Cu2(PySc)2Br2] middotH2O (5), [Cu(PySc)(NCS)] middot2H2O (6) and [Cu2(PySc)2(N3)2] (7) with 2-pyridinecarboxaldehyde-N4-phenylsemicarbazone (HPySc) have been prepared and character-ized using different analytical and spectroscopic techniques. The complex 6 is expected to be square planar while the other complexes are expected to be square pyramidal arrangement, among these, the geometry of complex 4 has been conformed by single crystal XRD study that it is a dimer and adopts distorted square pyramidal geometry around copper(II) centre. All the complexes are found to be para-magnetic and non-conductive in nature. The semicarbazone ligand is coordinated in neutral form in two of the complexes and in ionic form in others. DFT/B3LYP/6-311g **/LANL2DZ computations of the ligand HpySc (PyCHNNCONHPh) and seven Cu(II) complexes were performed to analyze the FMOs and impor-tant electron delocalizations that existed in each compound. Molecular stability and bond strengths have been investigated by applying natural bond orbital (NBO) analysis. All the complexes are more stable than the semicarbazone and the complex 2 is the most electronically stable (-5.160 eV) among the com-plexes. Furthermore, the semicarbazone is the hardest and complex 5 is the softest than all complexes due to the eta values. The calculated energy gap between HOMO and LUMO energies show the variations of nucleophilic and electrophilic reactivity regions in the semicarbazone and in complexes 1-7.(c) 2022 Elsevier B.V. All rights reserved.

引用

页数：15

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