Synthesis and Fluorescence Properties of Structurally Characterized Heterobimetalic Cu(II)⁻Na(I) Bis(salamo)-Based Complex Bearing Square Planar, Square Pyramid and Triangular Prism Geometries of Metal Centers

• Published in: Molecules (Basel, Switzerland) Vol. 23; no. 5; p. 1006
• Main Authors: Dong, Xiu-Yan, Zhao, Qing, Wei, Zhi-Li, Mu, Hao-Ran, Zhang, Han, Dong, Wen-Kui
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 25.04.2018; MDPI
• Subjects: Chloroform; Coordination Complexes - chemical synthesis; Coordination Complexes - chemistry; Copper; Copper - chemistry; crystal structure; Crystallography, X-Ray; Diffraction; Fluorescence; Geometry; heterobimetalic complex; Ligands; Metals; Models, Molecular; Molecular Structure; Oximes - chemistry; Single crystals; Sodium - chemistry; Spectrometry, Fluorescence; spectroscopic study; symmetric bis(salamo)-type tetraoxime; synthesis; X-ray diffraction; synthesis; crystal structure; heterobimetalic complex; spectroscopic study; symmetric bis(salamo)-type tetraoxime
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules23051006

A novel heterotrinuclear complex [Cu₂(L)Na( -NO₃)]∙CH₃OH∙CHCl₃ derived from a symmetric bis(salamo)-type tetraoxime H₄L having a naphthalenediol unit, was prepared and structurally characterized via means of elemental analyses, UV-Vis, FT-IR, fluorescent spectra and single-crystal X-ray diffraction. The heterobimetallic Cu(II)⁻Na(I) complex was acquired via the reaction of H₄L with 2 equivalents of Cu(NO₃)₂·2H₂O and 1 equivalent of NaOAc. Clearly, the heterotrinuclear Cu(II)⁻Na(I) complex has a 1:2:1 ligand-to-metal (Cu(II) and Na(I)) ratio. X-ray diffraction results exhibited the different geometric behaviors of the Na(I) and Cu(II) atoms in the heterotrinuclear complex; the both Cu(II) atoms are sited in the N₂O₂ coordination environments of fully deprotonated (L) unit. One Cu(II) atom (Cu1) is five-coordinated and possesses a geometry of slightly distorted square pyramid, while another Cu(II) atom (Cu2) is four-coordination possessing a square planar coordination geometry. Moreover, the Na(I) atom is in the O₆ cavity and adopts seven-coordination with a geometry of slightly distorted single triangular prism. In addition, there are abundant supramolecular interactions in the Cu(II)⁻Na(I) complex. The fluorescence spectra showed the Cu(II)⁻Na(I) complex possesses a significant fluorescent quenching and exhibited a hypsochromic-shift compared with the ligand H₄L.