TY - JOUR
T1 - Electronic structures of octahedral Ni(II) complexes with "click" derived triazole ligands
T2 - A combined structural, magnetometric, spectroscopic, and theoretical study
AU - Schweinfurth, David
AU - Krzystek, J.
AU - Schapiro, Igor
AU - Demeshko, Serhiy
AU - Klein, Johannes
AU - Telser, Joshua
AU - Ozarowski, Andrew
AU - Su, Cheng Yong
AU - Meyer, Franc
AU - Atanasov, Mihail
AU - Neese, Frank
AU - Sarkar, Biprajit
PY - 2013/6/17
Y1 - 2013/6/17
N2 - The coordination complexes of Ni(II) with the tripodal ligands tpta (tris[(1-phenyl-1H-1,2,3-triazol-4-yl)methyl]amine), tbta ([(1-benzyl-1H-1,2,3- triazol-4-yl)methyl]amine), and tdta (tris[(1-(2,6-diisopropyl-phenyl)-1H-1,2,3- triazol-4-yl)methyl]amine) and the bidentate ligand pyta (1-(2,6- diisopropylphenyl)-4-(2-pyridyl)-1,2,3-triazole), [Ni(tpta)2](BF 4)2 (1), [Ni(tbta)2](BF4) 2 (2), [Ni(tdta)2](BF4)2 (3), and [Ni(pyta)3](BF4)2 (4), were synthesized from Ni(BF4)2·6H2O and the corresponding ligands. Complexes 2 and 4 were also characterized structurally using X-ray diffraction and magnetically via susceptibility measurements. Structural characterization of 2 that contains the potentially tetradentate, tripodal tbta ligand revealed that the Ni(II) center in that complex is in a distorted octahedral environment, being surrounded by two of the tripodal ligands. Each of those ligands coordinate to the Ni(II) center through the central amine nitrogen atom and two of the triazole nitrogen donors; the Ni-N(amine) distances being longer than Ni-N(triazole) distances. In case of 4, three of the bidentate ligands pyta bind to the Ni(II) center with the binding of the triazole nitrogen atoms being stronger than those of the pyridine. Temperature dependent susceptibility measurements on 2 and 4 revealed a room temperature χMT value of 1.18 and 1.20 cm3 K mol-1, respectively, indicative of S = 1 systems. High-frequency and -field EPR (HFEPR) measurements were performed on all the complexes to accurately determine their g-tensors and the all-important zero-field splitting (zfs) parameters D and E. Interpretation of the optical d-d absorption spectra using ligand field theory revealed the B and Dq values for these complexes. Quantum chemical calculations based on the X-ray and DFT optimized geometries and their ligand field analysis have been used to characterize the metal-ligand bonding and its influence on the magnitude and sign of the zfs parameters. This is the first time that such extensive HFEPR, LFT, and advanced computational studies are being reported on a series of mononuclear, distorted octahedral Ni(II) complexes containing different kinds of nitrogen donating ligands in the same complex.
AB - The coordination complexes of Ni(II) with the tripodal ligands tpta (tris[(1-phenyl-1H-1,2,3-triazol-4-yl)methyl]amine), tbta ([(1-benzyl-1H-1,2,3- triazol-4-yl)methyl]amine), and tdta (tris[(1-(2,6-diisopropyl-phenyl)-1H-1,2,3- triazol-4-yl)methyl]amine) and the bidentate ligand pyta (1-(2,6- diisopropylphenyl)-4-(2-pyridyl)-1,2,3-triazole), [Ni(tpta)2](BF 4)2 (1), [Ni(tbta)2](BF4) 2 (2), [Ni(tdta)2](BF4)2 (3), and [Ni(pyta)3](BF4)2 (4), were synthesized from Ni(BF4)2·6H2O and the corresponding ligands. Complexes 2 and 4 were also characterized structurally using X-ray diffraction and magnetically via susceptibility measurements. Structural characterization of 2 that contains the potentially tetradentate, tripodal tbta ligand revealed that the Ni(II) center in that complex is in a distorted octahedral environment, being surrounded by two of the tripodal ligands. Each of those ligands coordinate to the Ni(II) center through the central amine nitrogen atom and two of the triazole nitrogen donors; the Ni-N(amine) distances being longer than Ni-N(triazole) distances. In case of 4, three of the bidentate ligands pyta bind to the Ni(II) center with the binding of the triazole nitrogen atoms being stronger than those of the pyridine. Temperature dependent susceptibility measurements on 2 and 4 revealed a room temperature χMT value of 1.18 and 1.20 cm3 K mol-1, respectively, indicative of S = 1 systems. High-frequency and -field EPR (HFEPR) measurements were performed on all the complexes to accurately determine their g-tensors and the all-important zero-field splitting (zfs) parameters D and E. Interpretation of the optical d-d absorption spectra using ligand field theory revealed the B and Dq values for these complexes. Quantum chemical calculations based on the X-ray and DFT optimized geometries and their ligand field analysis have been used to characterize the metal-ligand bonding and its influence on the magnitude and sign of the zfs parameters. This is the first time that such extensive HFEPR, LFT, and advanced computational studies are being reported on a series of mononuclear, distorted octahedral Ni(II) complexes containing different kinds of nitrogen donating ligands in the same complex.
UR - http://www.scopus.com/inward/record.url?scp=84879245074&partnerID=8YFLogxK
U2 - 10.1021/ic3026123
DO - 10.1021/ic3026123
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AN - SCOPUS:84879245074
SN - 0020-1669
VL - 52
SP - 6880
EP - 6892
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 12
ER -