TY - JOUR
T1 - Hybrid molecular material exhibiting single-molecule magnet behavior and molecular conductivity
AU - Hiraga, Hiroki
AU - Miyasaka, Hitoshi
AU - Nakata, Kazuya
AU - Kajiwara, Takashi
AU - Takaishi, Shinya
AU - Oshima, Yugo
AU - Nojiri, Hiroyuki
AU - Yamashita, Masahiro
PY - 2007/11/12
Y1 - 2007/11/12
N2 - Two unique materials based on Mn4 single-molecule magnet (SMM) clusters (ST = 9) and integer or non-integer average valent platinum maleonitriledithiolate (mnt2-) complexes, [{MnII 2MnIII2(hmp)6(MeCN) 2}{Pt(mnt)2}2][Pt(mnt)2] 2· 2MeCN (1) and [{MnII2Mn III2(hmp)6(MeCN)2}{Pt(mnt) 2}4][Pt(mnt)2]2 (2), were synthesized by the material diffusion method and electrochemical oxidation, respectively (hmp- = 2-hydroxymethylpyridinate). 1 and 2 are comprised of four and six [Pt(mnt)2]n- units, respectively, in addition to a common MnII2Mn III2 double-cuboidal unit, [MnII 2-MnIII2(hmp)6(MeCN) 2]4+ (hereinafter [Mn4]4+). Among the [Pt(mnt)2]n- units, two units in 1 and four units in 2 are coordinated with the [Mn4]4+ unit, forming a 1D chain of {-[Mn4]-[Pt(mnt)2]2-} for 1 and a discrete subunit of {[Pt(mnt)2]2-[Mn4]-[Pt(mnt) 2]2} for 2. The other two [Pt(mnt)2] n- units, occupying void space of the packing, form a stacking column with the coordinating [Pt(mnt)2]n- units, finally constructing hybrid frames of aggregates consisting of [Mn4] 4+ units and [Pt(mnt)2]n- units. Electronic conductivity measurements revealed that 1 is an insulator and 2 is a semiconductor with σ = 0.22 S·cm-1 at room temperature and an activation energy of 136 meV. Detailed magnetic measurements proved that the [Mn4]4+ units in 1 and 2 behave as SMMs with an S T = 9 ground state at low temperatures. There is no significant interaction between [Mn4]4+ units and [Pt(mnt) 2]n- units, but interactions between localized spins of [Pt(mnt)2]n- were detected even in 2 at low temperatures where the conductivity is electronically insulated. 2 is the first example of a hybridized material exhibiting SMM behavior and electronic conductivity.
AB - Two unique materials based on Mn4 single-molecule magnet (SMM) clusters (ST = 9) and integer or non-integer average valent platinum maleonitriledithiolate (mnt2-) complexes, [{MnII 2MnIII2(hmp)6(MeCN) 2}{Pt(mnt)2}2][Pt(mnt)2] 2· 2MeCN (1) and [{MnII2Mn III2(hmp)6(MeCN)2}{Pt(mnt) 2}4][Pt(mnt)2]2 (2), were synthesized by the material diffusion method and electrochemical oxidation, respectively (hmp- = 2-hydroxymethylpyridinate). 1 and 2 are comprised of four and six [Pt(mnt)2]n- units, respectively, in addition to a common MnII2Mn III2 double-cuboidal unit, [MnII 2-MnIII2(hmp)6(MeCN) 2]4+ (hereinafter [Mn4]4+). Among the [Pt(mnt)2]n- units, two units in 1 and four units in 2 are coordinated with the [Mn4]4+ unit, forming a 1D chain of {-[Mn4]-[Pt(mnt)2]2-} for 1 and a discrete subunit of {[Pt(mnt)2]2-[Mn4]-[Pt(mnt) 2]2} for 2. The other two [Pt(mnt)2] n- units, occupying void space of the packing, form a stacking column with the coordinating [Pt(mnt)2]n- units, finally constructing hybrid frames of aggregates consisting of [Mn4] 4+ units and [Pt(mnt)2]n- units. Electronic conductivity measurements revealed that 1 is an insulator and 2 is a semiconductor with σ = 0.22 S·cm-1 at room temperature and an activation energy of 136 meV. Detailed magnetic measurements proved that the [Mn4]4+ units in 1 and 2 behave as SMMs with an S T = 9 ground state at low temperatures. There is no significant interaction between [Mn4]4+ units and [Pt(mnt) 2]n- units, but interactions between localized spins of [Pt(mnt)2]n- were detected even in 2 at low temperatures where the conductivity is electronically insulated. 2 is the first example of a hybridized material exhibiting SMM behavior and electronic conductivity.
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U2 - 10.1021/ic700727n
DO - 10.1021/ic700727n
M3 - Article
C2 - 17948984
AN - SCOPUS:36349006937
SN - 0020-1669
VL - 46
SP - 9661
EP - 9671
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 23
ER -