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  Electronic Structures of Octahedral Ni(II) Complexes with “Click” Derived Triazole Ligands: A Combined Structural, Magnetometric, Spectroscopic, and Theoretical Study

Schweinfurth, D., Krzystek, J., Schapiro, I., Demeshko, S., Klein, J., Telser, J., et al. (2013). Electronic Structures of Octahedral Ni(II) Complexes with “Click” Derived Triazole Ligands: A Combined Structural, Magnetometric, Spectroscopic, and Theoretical Study. Inorganic Chemistry, 52(12), 6880-6892. doi:10.1021/ic3026123.

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Schweinfurth, David1, Author
Krzystek, J.2, Author
Schapiro, Igor3, Author              
Demeshko, Serhiy4, Author
Klein, Johannes5, Author
Telser, Joshua6, Author
Ozarowski, Andrew2, Author
Su, Cheng-Yong7, Author
Meyer, Franc4, Author
Atanasov, Mihail3, 8, Author              
Neese, Frank3, Author              
Sarkar, Biprajit1, Author
1Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstraße 34-36, D-14195 Berlin, Germany, ou_persistent22              
2National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States, ou_persistent22              
3Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
4Institut für Anorganische Chemie, Georg-August Universität Göttingen, Tammanstraße 4, D-37077 Göttingen, Germany, ou_persistent22              
5Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany, ou_persistent22              
6Department of Biological, Chemical and Physical Sciences, Roosevelt University, Chicago, Illinois 60605, United States, ou_persistent22              
7Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China, ou_persistent22              
8Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria, ou_persistent22              


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 Abstract: 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](BF4)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.


Language(s): eng - English
 Dates: 2012-11-292013-05-232013-06-17
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ic3026123
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 52 (12) Sequence Number: - Start / End Page: 6880 - 6892 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669