Syntheses, crystal structures and spectroscopy of di/tri/tetranuclear discrete and co-crystalline copper(II)-Na^I/Zn^II/Cd^II complexes derived from a compartmental ligand: Inconsistency in the shifting of the copper(II) d-d

详细信息    查看全文

• 作者：Sagarika Bhattacharya ; Arpita Jana ; Sasankasekhar Mohanta
• 关键词：Compartmental ligand ; Crystal structure ; Heteronuclear ; Co-crystal ; Spectroscopy ; Blue shifting
• 刊名：Polyhedron
• 出版年：2013
• 出版时间：7 October, 2013
• 年：2013
• 卷：62
• 期：Complete
• 页码：234-242
• 全文大小：1598 K

文摘

The work in this report presents the syntheses, characterization, crystal structures and electronic spectra of the six heteronuclear complexes [Cu^IIL¹Na^I(¦Ì-BF₄)₂Na^IL¹Cu^II]¡¤2CH₃COCH₃ (1), [Cu^IIL¹Na^I(NO₃)(MeOH)] (2), [Cu^IIL¹Zn^II(H₂O)₂L¹Cu^II](ClO₄)₂ (3), [Cu^II(MeOH)L¹Zn^IICl₂] (4), [Cu^IIL¹Cd^II(H₂O)(MeOH)₂](ClO₄)₂ (5) and [Cu^IIL¹Cd^IICl₂(MeOH)]¡¤[Cu^II(MeOH)L¹Cd^IICl₂] (6), where H₂L¹ is N,N¡ä-ethylenebis(3-methoxysalicylaldimine). The crystal systems and space groups are as follows: 1 and 2, triclinic, ; 3 and 6, monoclinic, P2₁/c; 4, orthorhombic, P2₁2₁2₁; 5, monoclinic, C2/c. While the N(imine)₂O(phenoxo)₂ compartment accommodates the copper(II) center, the larger and open O(phenoxo)₂O(methoxy)₂ compartment interacts with the second metal ion. Compounds 2, 4 and 5 are diphenoxo-bridged dinuclear systems, compound 3 is a trinuclear system in which the two Cu^IIZn^II pairs are monophenoxo-bridged, compound 1 is a tetranuclear system in which two diphenoxo-bridged Cu^IINa^I units are interlinked by two tetrafluoroborate moieties, and compound 6 is a [2¡Á1+2¡Á1] co-crystal of two dinuclear Cu^IICd^II units. The solid state electronic spectra of compounds 1-6 and also the mononuclear compound [Cu^IIL¹(H₂O)] have been recorded in the range 400-800 nm. While correlating the d-d band position with the structural parameters and a previously proposed correlation, some inconsistency has been found, indicating that this area should be explored further.