TY - JOUR
T1 - Novel Supramolecular Assemblies of Co(III) & Cu(II) with Diethylenetriamine and Azide
T2 - Synthesis, Structure, Spectroscopic and Magnetic Studies
AU - Pandey, Priyanka
AU - Cosquer, Goulven
AU - Yamashita, Masahiro
AU - Sunkari, Sailaja S.
PY - 2018/2/28
Y1 - 2018/2/28
N2 - In exploring the role of increased ligand basicity as well as denticity on moving from ethylenediamine (en) or 1,3-diaminopropane (1,3-dap), on supramolecular solid formation, complexation involving diethylenetriamine (det) and azide with CoII and CuII afforded three new complexes [Co(det)2](N3)3 (1), [Co(det)(N3)3] (2) and [Cu2(det)2(N3)5(H2O)2Na] (3) under self assembling conditions and are characterized structurally and magnetically. Formation of 1 and 2 is sensitive to temperature of crystallization, while such a temperature influence could not be observed for CuII system due to lack of crystals at low temperatures. As expected with a tridentate ligand, strong chelation stabilizes 1 at LT and is a thermodynamically stable product, while isolation of 2 at RT conditions is under kinetic control. Decomposition of 2 at high temperatures (above 70 °C) as revealed through temperature dependent UV-vis spectral studies also confirms its instability. Presence of three donor sites of det, leads to interesting structural pattern in Jahn-Teller active CuII, resulting in cationic chains of [Cu(det)(N3)]n + bridged by μ-1,3 azido bridges to the neighboring [Na(H2O)2(N3)2]− units, thus leading to a 2-D assembly of alternating layers of cationic and anionic chains in the unit cell of 3. Magnetic studies of 3 reveals anti-ferromagnetic interaction between the copper ions (J=– 0.479 cm–1), in conformity with the bridge angle dependent magnetic behavior in azido bridged copper complexes.
AB - In exploring the role of increased ligand basicity as well as denticity on moving from ethylenediamine (en) or 1,3-diaminopropane (1,3-dap), on supramolecular solid formation, complexation involving diethylenetriamine (det) and azide with CoII and CuII afforded three new complexes [Co(det)2](N3)3 (1), [Co(det)(N3)3] (2) and [Cu2(det)2(N3)5(H2O)2Na] (3) under self assembling conditions and are characterized structurally and magnetically. Formation of 1 and 2 is sensitive to temperature of crystallization, while such a temperature influence could not be observed for CuII system due to lack of crystals at low temperatures. As expected with a tridentate ligand, strong chelation stabilizes 1 at LT and is a thermodynamically stable product, while isolation of 2 at RT conditions is under kinetic control. Decomposition of 2 at high temperatures (above 70 °C) as revealed through temperature dependent UV-vis spectral studies also confirms its instability. Presence of three donor sites of det, leads to interesting structural pattern in Jahn-Teller active CuII, resulting in cationic chains of [Cu(det)(N3)]n + bridged by μ-1,3 azido bridges to the neighboring [Na(H2O)2(N3)2]− units, thus leading to a 2-D assembly of alternating layers of cationic and anionic chains in the unit cell of 3. Magnetic studies of 3 reveals anti-ferromagnetic interaction between the copper ions (J=– 0.479 cm–1), in conformity with the bridge angle dependent magnetic behavior in azido bridged copper complexes.
KW - Azide
KW - Cobalt (III)
KW - Copper(II)
KW - Diethylenetriamine
KW - Magnetic study
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U2 - 10.1002/slct.201702715
DO - 10.1002/slct.201702715
M3 - Article
AN - SCOPUS:85042635421
VL - 3
SP - 2240
EP - 2244
JO - ChemistrySelect
JF - ChemistrySelect
SN - 2365-6549
IS - 8
ER -