TY - JOUR
T1 - Hybridized complexes of [MnIII2] single-molecule magnets and Ni dithiolate complexes
AU - Hiraga, Hiroki
AU - Miyasaka, Hitoshi
AU - Takaishi, Shinya
AU - Kajiwara, Takashi
AU - Yamashita, Masahiro
N1 - Funding Information:
We acknowledge Professor Dr. T. Kuroda-Sowa at Kinki University, Osaka Japan for simulating MH curves. This work was financially supported by the CREST project, Japan Science and Technology Agency (JST), and by a Grant-in-Aid for Scientific Research (Grant No. 18685007) on Priority Areas (Grant No. 18033042 “Chemistry of Coordination Space”) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan (H.M.).
PY - 2008/10/1
Y1 - 2008/10/1
N2 - The electrochemical oxidation of an acetone solution or acetonitrile (MeCN) solution containing [MnIII2 (5 -MeOsaltmen)2 (H2 O)2](PF6)2 (5-MeOsaltmen2- = N,N′-(1,1,2,2-tetramethylethylene)bis(5-methoxysalicylideneiminate)) and (NBu4)[Ni(dmit)2] (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate) has yielded two unique hybrid materials in which [Mn2]2+ single-molecule magnets (SMMs) possessing an ST = 4 ground state and [Ni(dmit)2]n- molecules each possessing an average valence of ca.-0.29 are aggregated in a layer-by-layer form; [Mn2(5-MeOsaltmen)2(acetone)2][Ni(dmit)2]7 · 4acetone (1) and [Mn2(5-MeOsaltmen)2(MeCN)2][Ni(dmit)2]7 · 4MeCN (2).Compounds 1 and 2 have a similar structure to each other and crystallize in the triclinic P over(1, ̄) space group with inversion centers on the midpoint of Mn⋯Mn vector of the dimer and a Ni ion of one of [Ni(dmit)2]0.29- molecules (i.e., Z = 1).The [Mn2]2+ unit has a typical Mn(III) out-of-plane dimeric core and is structurally consistent with the already reported [Mn2] SMMs.Seven [Ni(dmit)2]0.29- units in the formula have a square-planar coordination geometry in common, and the charge distribution among them can be averagely assigned according to their local structures and IR spectra; thus, the formal charge for each molecule is -0.29.These two kinds of molecules,[Mn2]2+ SMM units and [Ni(dmit)2]0.29- units, construct hybrid frames aggregating individually, where the latter units form a β-type stacking arrangement. Electronic conductivity measurements revealed that 1 and 2 are semiconductors with σrt = 1.6 S cm-1 and 2.8 S cm-1, respectively, at room temperature. The detail magnetic measurements proved that the [Mn2]2+ units in 1 and 2 behave as ST = 4 SMMs at low temperatures, although their conductivities are already insulated at such temperatures.
AB - The electrochemical oxidation of an acetone solution or acetonitrile (MeCN) solution containing [MnIII2 (5 -MeOsaltmen)2 (H2 O)2](PF6)2 (5-MeOsaltmen2- = N,N′-(1,1,2,2-tetramethylethylene)bis(5-methoxysalicylideneiminate)) and (NBu4)[Ni(dmit)2] (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate) has yielded two unique hybrid materials in which [Mn2]2+ single-molecule magnets (SMMs) possessing an ST = 4 ground state and [Ni(dmit)2]n- molecules each possessing an average valence of ca.-0.29 are aggregated in a layer-by-layer form; [Mn2(5-MeOsaltmen)2(acetone)2][Ni(dmit)2]7 · 4acetone (1) and [Mn2(5-MeOsaltmen)2(MeCN)2][Ni(dmit)2]7 · 4MeCN (2).Compounds 1 and 2 have a similar structure to each other and crystallize in the triclinic P over(1, ̄) space group with inversion centers on the midpoint of Mn⋯Mn vector of the dimer and a Ni ion of one of [Ni(dmit)2]0.29- molecules (i.e., Z = 1).The [Mn2]2+ unit has a typical Mn(III) out-of-plane dimeric core and is structurally consistent with the already reported [Mn2] SMMs.Seven [Ni(dmit)2]0.29- units in the formula have a square-planar coordination geometry in common, and the charge distribution among them can be averagely assigned according to their local structures and IR spectra; thus, the formal charge for each molecule is -0.29.These two kinds of molecules,[Mn2]2+ SMM units and [Ni(dmit)2]0.29- units, construct hybrid frames aggregating individually, where the latter units form a β-type stacking arrangement. Electronic conductivity measurements revealed that 1 and 2 are semiconductors with σrt = 1.6 S cm-1 and 2.8 S cm-1, respectively, at room temperature. The detail magnetic measurements proved that the [Mn2]2+ units in 1 and 2 behave as ST = 4 SMMs at low temperatures, although their conductivities are already insulated at such temperatures.
KW - Hybridized compounds
KW - Manganese(III) salen-type complex
KW - Molecular conductors
KW - Nickel dithiolene complex
KW - Single-molecule magnets
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U2 - 10.1016/j.ica.2008.02.070
DO - 10.1016/j.ica.2008.02.070
M3 - Article
AN - SCOPUS:49549098427
SN - 0020-1693
VL - 361
SP - 3863
EP - 3872
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 14-15
ER -