Synthesis, crystal structure, thermal decomposition, and XPS studies of homo and heterotrinuclear Cu(II)–Cu(II)–Cu(II) and Cu(II)–Ni(II)–Cu(II) complexes obtained from salpn type ligands

• Published in: Russian journal of coordination chemistry Vol. 43; no. 7; pp. 463 - 472
• Main Authors: Acar, N., Atakol, O., Dinçer Kaya, F. N., Svoboda, I., Yazıcıoğlu, M., Öz, S.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 01.07.2017; Springer Nature B.V
• Subjects: Chemistry; Chemistry and Materials Science; Copper; Crystal structure; Distortion; Infrared radiation; Infrared spectroscopy; Inorganic Chemistry; Ligands; Nickel; Nuclei; Physical Chemistry; Spectroscopic analysis; Thermal decomposition; Thermal degradation; Water chemistry; X ray photoelectron spectroscopy; X-ray diffraction; XPS study; binding energy; salpn type Schiff base; reduced Schiff base; heterotrinuclear complex
• ISSN: 1070-3284; 1608-3318
• DOI: 10.1134/S1070328417070028

In this study, a mononuclear CuL complex was prepared by the use of bis- N , N ′-(salicylidene)-1, 3-propanediamine (LH 2 ) and Cu 2+ ion. NiCl 2 and NiBr 2 salt were treated with this complex in dioxanewater medium and two new complexes [(CuL) 2 NiCl 2 (H 2 O) 2 ] and [(CuL) 2 NiBr 2 (H 2 O) 2 )] with Cu(II)–Ni(II)–Cu(II) nucleus structure were obtained. In addition to this bis- N , N ′-(2-hydroxybenzyl)-1,3-diaminopropane (L H H 2 ) was prepared by the reduction of LH 2 with NaBH 4 in MeOH medium. The treatment of this reduced complex with Cu 2+ ion resulted a complex [(CuL H ) 2 CuCl 2 ] with a structure of Cu(II)–Cu(II)–Cu(II). The complexes prepared were characterized by the use of elemental analysis, IR spectroscopy, thermogravimetric and X-ray diffraction methods. The crystal structures of [(CuL) 2 NiBr 2 (H 2 O) 2 ] (СIF file CCDC 1448402) and [(CuL H ) 2 CuCl 2 ] (СIF file CCDC 1448401) complexes were elucidated. It was found that halogen ions are coordinated to terminal Cu 2+ ions which are in a distorted square pyramid coordination sphere. It was determined that the central Cu(II), which joins terminal square pyramidal Cu(II), was coordinated only by the phenolic oxygens of the ligand while the central Ni(II) was coordinated by two phenolic oxygens of the organic ligand and two water molecules. These complexes were investigated by XPS and it was found that the terminal and central Cu 2+ ions were different in Cu(II)–Cu(II)–Cu(II) complex. Also, the thermal degradation of the CuLH complex unit was observed to exothermic in contrast to the expectations.