Structure and Magnetic Properties of (meso-Tetraphenylporphinato)manganese(III) Bis(dithiolato)nickelates
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- 作者：Louise N. Dawe ; Jesse Miglioi ; Laura Turnbow ; Michelle L. Taliaferro ; William W. Shum ; Joshua D. Bagnato ; Lev N. Zakharov ; Arnold L. Rheingold ; Atta M. Arif ; Marc Fourmigué ; and Joel S. Miller
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：October 17, 2005
- 年：2005
- 卷：44
- 期：21
- 页码：7530 - 7539
- 全文大小：772K
- 年卷期：v.44,no.21(October 17, 2005)
- ISSN：1520-510X
文摘
The crystal structures of [MnTPP]{Ni[S2C2H(CN)]2} [MnTPP = (meso-tetraphenylporphinato)manganese(III)] and[MnTPP]{Ni[S2C2(CN)2]2} have been determined. These salts possess trans-
-coordination of S = 1/2{Ni[S2C2H(CN)]2}
- and {Ni[S2C2(CN)2]2}- to Mn(III) and form parallel 1-D coordination polymer chains exhibiting
CN at 2210 and 2200 and 2220 and 2212 cm-1, respectively. The bis(dithiolato) monoanions are planar andbridge two cations with MnN distances of 2.339(16), and 2.394(3) Å, respectively, which are comparable to relatedMnN distances observed for [MnTPP][TCNE]·x(solvates). In addition, [MnTP'P]{Ni[S2C2(CN)2]2} {H2TP'P = meso-tetrakis[3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin] and [MnTP'P(OH2)]{Ni[S2C2(CN)2]2} were prepared. The latterforms isolated paramagnetic ions. The room-temperature values of 
T for 1-D [MnTPP]{Ni[S2C2H(CN)]2}, [MnTPP]{Ni[S2C2(CN)2]2}, and [MnTP'P]{Ni[S2C2(CN)2]2} are 2.55, 3.28, and 2.86 emu K/mol, respectively. Susceptibility() measurements between 2 and 300 K reveal weak antiferromagnetic interactions with 
= -5.9 and -0.2 K for[MnTPP]{Ni[S2C2H(CN)]2} and [MnTPP]{Ni[S2C2(CN)2]2}, respectively, and stronger antiferromagnetic coupling of-50 K for [MnTP'P]{Ni[S2C2(CN)2]2} from fits of (T) to the Curie-Weiss law. The 1-D intrachain coupling, Jintra,of [MnTPP]{Ni[S2C2H(CN)]2} and [MnTPP]{Ni[S2C2(CN)2]2} was determined from modeling T(T) by the Seidenexpression (H = -2JSi·Sj) with J/kB = -8.00 K (-5.55 cm-1; -0.65 meV) for [MnTPP]{Ni[S2C2H(CN)]2}, J/kB =-3.00 K (-2.08 cm-1; -0.25 meV) for [MnTP'P]{Ni[S2C2(CN)2]2}, and J/kB = -122 K (-85 cm-1) for [MnTP'P]{Ni[S2C2(CN)2]2}. These observed negative Jintra/kB values are indicative of antiferromagnetic coupling. These materialsorder as ferrimagnets at 5.5, 2.3, and 8.0 K, for [MnTPP]{Ni[S2C2H(CN)]2}, [MnTPP]{Ni[S2C2(CN)2]2}, and [MnTP'P]{Ni[S2C2(CN)2]2}, respectively, based upon the temperature at which maximum in the 10 Hz '(T) data occurs.[MnTP'P]{Ni[S2C2(CN)2]2} has a coercivity of 17 700 Oe and remanent magnetizations of 7250 emu Oe/mol at 2K and 17 Oe and 850 emu Oe/mol at 5 K; hence, upon cooling it goes from being a soft magnet to being a veryhard magnet.
-coordination of S = 1/2{Ni[S2C2H(CN)]2}- and {Ni[S2C2(CN)2]2}- to Mn(III) and form parallel 1-D coordination polymer chains exhibitingCN at 2210 and 2200 and 2220 and 2212 cm-1, respectively. The bis(dithiolato) monoanions are planar andbridge two cations with MnN distances of 2.339(16), and 2.394(3) Å, respectively, which are comparable to relatedMnN distances observed for [MnTPP][TCNE]·x(solvates). In addition, [MnTP'P]{Ni[S2C2(CN)2]2} {H2TP'P = meso-tetrakis[3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin] and [MnTP'P(OH2)]{Ni[S2C2(CN)2]2} were prepared. The latterforms isolated paramagnetic ions. The room-temperature values of T for 1-D [MnTPP]{Ni[S2C2H(CN)]2}, [MnTPP]{Ni[S2C2(CN)2]2}, and [MnTP'P]{Ni[S2C2(CN)2]2} are 2.55, 3.28, and 2.86 emu K/mol, respectively. Susceptibility() measurements between 2 and 300 K reveal weak antiferromagnetic interactions with = -5.9 and -0.2 K for[MnTPP]{Ni[S2C2H(CN)]2} and [MnTPP]{Ni[S2C2(CN)2]2}, respectively, and stronger antiferromagnetic coupling of-50 K for [MnTP'P]{Ni[S2C2(CN)2]2} from fits of (T) to the Curie-Weiss law. The 1-D intrachain coupling, Jintra,of [MnTPP]{Ni[S2C2H(CN)]2} and [MnTPP]{Ni[S2C2(CN)2]2} was determined from modeling T(T) by the Seidenexpression (H = -2JSi·Sj) with J/kB = -8.00 K (-5.55 cm-1; -0.65 meV) for [MnTPP]{Ni[S2C2H(CN)]2}, J/kB =-3.00 K (-2.08 cm-1; -0.25 meV) for [MnTP'P]{Ni[S2C2(CN)2]2}, and J/kB = -122 K (-85 cm-1) for [MnTP'P]{Ni[S2C2(CN)2]2}. These observed negative Jintra/kB values are indicative of antiferromagnetic coupling. These materialsorder as ferrimagnets at 5.5, 2.3, and 8.0 K, for [MnTPP]{Ni[S2C2H(CN)]2}, [MnTPP]{Ni[S2C2(CN)2]2}, and [MnTP'P]{Ni[S2C2(CN)2]2}, respectively, based upon the temperature at which maximum in the 10 Hz '(T) data occurs.[MnTP'P]{Ni[S2C2(CN)2]2} has a coercivity of 17 700 Oe and remanent magnetizations of 7250 emu Oe/mol at 2K and 17 Oe and 850 emu Oe/mol at 5 K; hence, upon cooling it goes from being a soft magnet to being a veryhard magnet.