New classes of organic Chelate-Free coordination Polymers: An End-On Azido-Bridged Cu(II) 1-D chain composed of {Cu6(N3)12} repeating units. (15th September 2021)

• Record Type: Journal Article
• Authors: Papanikolaou, Gavriilia T.; Pantelis, Konstantinos N.; Lazari, Gerasimi; Cunha-Silva, Luis; Escuer, Albert; Stamatatos, Theocharis C.
• Is Part Of: Polyhedron. Volume 206(2021)
• Publication Date: 2021-09-15
• Subjects: Copper -- Azides -- Coordination polymers -- Crystal structures -- Magnetic properties; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2021.115315
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: A structurally new 1-D coordination polymer composed of {Cu6 (N3 )12 } repeating units was prepared by the organic chelate-free reaction between Cu(ClO4 )2 ·6H2 O and Me3 SiN3, in the presence of base NEt3 ; the reported compound is a rare example of azido-only bridged molecular material. Highlights: The use of Me3 SiN3 has led to an unusual 1-D polymer composed of {Cu6 (N3 )12 } repeating units. The metal ions are exclusively bridged by μ3 -1, 1, 1 and μ-1, 1 end-on N3 – groups. IR spectroscopic data fully support the presence of end-on azides. Magnetic susceptibility measurements revealed a local S = 0 spin for the {Cu6 (N3 )12 } repeating units. Abstract: The use of Me3 SiN3 in Cu II chemistry, under basic conditions, in the absence of any ancillary organic chelate, has led to an unusual 1-D coordination polymer (1 ) composed of {Cu6 (N3 )12 } repeating units. The metal ions in 1 are exclusively bridged by μ3 -1, 1, 1 and μ-1, 1 end-on N3 – groups. Peripheral ligation about the {Cu6 (N3 )12 } core is provided by eight MeCN solvate molecules. IR and UV/Vis spectroscopic data fully support the presence of end-on azides and d-d transitions of the metal ions, respectively. Magnetic susceptibility measurements revealed a continuous drop of the χ Μ Τ product and an overall antiferromagnetic response, which results in a local S = 0 spin for the {Cu6 (N3 )12 } repeating units of 1 . The combined results demonstrate the flexibility of this synthetic approach to purely inorganic-bridged coordination complexes (clusters and polymers) and its ability to yield new molecule-based materials with several potential applications, i.e., in molecular magnetism, catalysis, high energy materials and photochemistry.