Structure, magnetic properties and DFT calculations of azido-copper(ii) complexes with different azido-bonding, nuclearity and dimensionality

Abstract

Cu(ii) compounds derived from diamine substituted alkyl or phenyl groups with azido acting as the bridging ligand were synthesized and were structurally and magnetically characterized.

Steric Effects of Alkyl Substituents at N-Donor Bidentate Amines Direct the Nuclearity, Bonding and Bridging Modes in Isothiocyanato-Copper(II) Coordination Compounds

“…The coordination compounds were also characterized by IR, UV-Vis, and by single crystal X-ray crystallography. Probably, it is interesting to mention that although the µ-1,3and µ-1,1-bonding modes are common in bridging-azido-metal(II) coordination compounds [8,9,11,12,[14][15][16], the corresponding µ-1,1-bonding in the bridging-isothiocyanato compounds is rare [32][33][34] and in most cases alternating µ-1,3-bonding chains are observed [1][2][3][4][5][6][7]17,[21][22][23][24][25][26][27][28][29][30][31].…”

“…Pseudohalides are a class of compounds that are able to simultaneously bind two or more metal ions leading to the formation of di-or poly-nuclear coordination compounds of different nuclearity and clusters, and coordination polymers (CPs) of different dimensionality (1D, 2D, 3D) and topology [1][2][3][4][5][6][7][8][9][10]. However, the formation of these compounds depends largely on a number of factors which include the electronic nature and oxidation state of the metal ion, the nature of the coordinated ancillary co-ligand(s), its skeletal structure, and the steric hindrance imposed by the blocking co-ligand(s) surrounding the central metal ion [11,12].…”

“…However, the formation of these compounds depends largely on a number of factors which include the electronic nature and oxidation state of the metal ion, the nature of the coordinated ancillary co-ligand(s), its skeletal structure, and the steric hindrance imposed by the blocking co-ligand(s) surrounding the central metal ion [11,12]. Steric effects caused by the coordinating blocking ligands in coordination compounds have been reported to produce a dramatic effect on the structural and magnetic behavior of pseudohalide coordination compounds [1][2][3][4][5][6][7][8][9][10][11][13][14][15][16] but also in the biological catalytic reactions of the P-O bond cleavage in DNA and phosphodiester hydrolysis [17][18][19][20].…”

“…Crystals 2019, 9, x FOR PEER REVIEW 2 of 16 dramatic effect on the structural and magnetic behavior of pseudohalide coordination compounds [1][2][3][4][5][6][7][8][9][10][11][13][14][15][16] but also in the biological catalytic reactions of the P-O bond cleavage in DNA and phosphodiester hydrolysis [17][18][19][20]. Isothiocyanato coordination compounds are considered as among the most studied systems in coordination chemistry due to the diverse bonding properties of the NCS − ion as an ambidentate and bridging ligand that can bind two or more metal ions simultaneously as well as its ability to propagate magnetic interaction between bridged paramagnetic metal ions.…”

“…Anal. Calcd for C9 H 18 CuN 4 S 2 (MM = 309.94 g/mol): C, 34.88; H, 5.85; N, 18.08%. Found: C, 34.67; H, 5.55; N, 18.30%.…”