%0 Journal Article %1 AK53 %A Mondal, Suraj %A Mandal, Shuvankar %A Carrella, Luca %A Jana, Arpita %A Fleck, Michel %A Köhn, Andreas %A Rentschler, Eva %A Mohanta, Sasankasekhar %D 2015 %J Inorg. Chem. %K chemie imported koehn köhn from:alexanderdenzel theoretische stuttgart theochem %N 1 %P 117–131 %R 10.1021/ic501900d %T A series of MIICuII3stars (M = Mn, Ni, Cu, Zn) exhibiting unusual magnetic properties %U http://dx.doi.org/10.1021/ic501900d %V 54 %X The work in this report describes the syntheses, electrospray ionization mass spectrometry, structures, and exptl. and d. functional theor. (DFT) magnetic properties of four tetrametallic stars of compn. ［MII(CuIIL)3］(ClO4)2 (1, M = Mn; 2, M = Ni; 3, M = Cu; 4, M = Zn) derived from a single-compartment Schiff base ligand, N,N'-bis(salicylidene)-1,4-butanediamine (H₂L), which is the ［2 + 1］ condensation product of salicylaldehyde and 1,4-diaminobutane. The central metal ion (MnII, NiII, CuII, or ZnII) is linked with two μ2-phenoxo bridges of each of the three ［CuIIL］ moieties, and thus the central metal ion is encapsulated in between three ［CuIIL］ units. The title compds. are rare or sole examples of stars having these metal-ion combinations. In the cases of 1, 3, and 4, the four metal ions form a centered isosceles triangle, while the four metal ions in 2 form a centered equilateral triangle. Both the variable-temp. magnetic susceptibility and variable-field magnetization (at 2-10 K) of 1-3 were measured and simulated contemporaneously. While the MnIICuII3 compd. 1 exhibits ferromagnetic interaction with J = 1.02 cm-1, the NiIICuII3 compd. 2 and CuIICuII3 compd. 3 exhibit antiferromagnetic interaction with J = -3.53 and -35.5 cm-1, resp. Variable-temp. magnetic susceptibility data of the ZnIICuII3 compd. 4 indicate very weak antiferromagnetic interaction of -1.4 cm-1, as expected. On the basis of known correlations, the magnetic properties of 1-3 are unusual; it seems that ferromagnetic interaction in 1 and weak/moderate antiferromagnetic interaction in 2 and 3 are possibly related to the distorted coordination environment of the peripheral copper(II) centers (intermediate between square-planar and tetrahedral). DFT calcns. were done to elucidate the magnetic properties. The DFT-computed J values are quant. (for 1) or qual. (for 2 and 3) matched well with the exptl. values. Spin densities and magnetic orbitals (natural bond orbitals) correspond well with the trend of obsd./computed magnetic exchange interactions. ［on SciFinder(R)］ %@ 0020-1669

@article{AK53, abstract = {The work in this report describes the syntheses, electrospray ionization mass spectrometry, structures, and exptl. and d. functional theor. (DFT) magnetic properties of four tetrametallic stars of compn. ［MII(CuIIL)3］(ClO4)2 (1, M = Mn; 2, M = Ni; 3, M = Cu; 4, M = Zn) derived from a single-compartment Schiff base ligand, N,N'-bis(salicylidene)-1,4-butanediamine (H₂L), which is the ［2 + 1］ condensation product of salicylaldehyde and 1,4-diaminobutane. The central metal ion (MnII, NiII, CuII, or ZnII) is linked with two μ2-phenoxo bridges of each of the three ［CuIIL］ moieties, and thus the central metal ion is encapsulated in between three ［CuIIL］ units. The title compds. are rare or sole examples of stars having these metal-ion combinations. In the cases of 1, 3, and 4, the four metal ions form a centered isosceles triangle, while the four metal ions in 2 form a centered equilateral triangle. Both the variable-temp. magnetic susceptibility and variable-field magnetization (at 2-10 K) of 1-3 were measured and simulated contemporaneously. While the MnIICuII3 compd. 1 exhibits ferromagnetic interaction with J = 1.02 cm-1, the NiIICuII3 compd. 2 and CuIICuII3 compd. 3 exhibit antiferromagnetic interaction with J = -3.53 and -35.5 cm-1, resp. Variable-temp. magnetic susceptibility data of the ZnIICuII3 compd. 4 indicate very weak antiferromagnetic interaction of -1.4 cm-1, as expected. On the basis of known correlations, the magnetic properties of 1-3 are unusual; it seems that ferromagnetic interaction in 1 and weak/moderate antiferromagnetic interaction in 2 and 3 are possibly related to the distorted coordination environment of the peripheral copper(II) centers (intermediate between square-planar and tetrahedral). DFT calcns. were done to elucidate the magnetic properties. The DFT-computed J values are quant. (for 1) or qual. (for 2 and 3) matched well with the exptl. values. Spin densities and magnetic orbitals (natural bond orbitals) correspond well with the trend of obsd./computed magnetic exchange interactions. ［on SciFinder(R)］}, added-at = {2019-02-06T13:16:27.000+0100}, author = {Mondal, Suraj and Mandal, Shuvankar and Carrella, Luca and Jana, Arpita and Fleck, Michel and K{\"{o}}hn, Andreas and Rentschler, Eva and Mohanta, Sasankasekhar}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/219261a5b30a48eb19e6c66043e6cbf1f/theochem}, doi = {10.1021/ic501900d}, interhash = {c6d7c012defae2e9402dfef169bdb026}, intrahash = {19261a5b30a48eb19e6c66043e6cbf1f}, isbn = {0020-1669}, issn = {1520510X}, journal = {Inorg. Chem.}, keywords = {chemie imported koehn köhn from:alexanderdenzel theoretische stuttgart theochem}, number = 1, pages = {117–131}, timestamp = {2019-02-06T12:16:27.000+0100}, title = {{A series of MIICuII3stars (M = Mn, Ni, Cu, Zn) exhibiting unusual magnetic properties}}, url = {http://dx.doi.org/10.1021/ic501900d}, volume = 54, year = 2015 }