Mn(5,10,15,20-tetrakis(p-methoxyphenyl)porphyrinato)(pyridine) | 67368-89-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: Mn(5,10,15,20-tetrakis(p-methoxyphenyl)porphyrinato)(pyridine)
• 英文别名: Mn(II)(tetrakis(4-methoxyphenyl)porphyrin)(py)
• CAS: 67368-89-2
• 化学式: C₅₃H₄₁MnN₅O₄
• 分子量: 866.878
• InChiKey: HJCDNWWNCGRDDC-HTMHXADGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Mn(5,10,15,20-tetrakis(p-methoxyphenyl)porphyrinato)(pyridine) 、 四氰基乙烯 以 甲苯 为溶剂， 生成 manganese(III) tetrakis(4-methoxyphenyl)porphyrin tetracyanoethenide * 2 toluene
  参考文献：
  名称：

  Structure and Magnetic Properties of Antiferromagnetic Manganese(III) Tetrakis(4- methoxyphenyl)porphyrin Tetracyanoethenide, [MnTOMePP][TCNE]·2PhMe, and Manganese(III) Tetrakis(2-fluorophenyl)porphyrin Tetracyanoethenide, [MnTFPP][TCNE]·2PhMe

  摘要：

  The tetracyanoethylene (TCNE) electron-transfer salts of meso-tetrakis(4-methoxyphenyl)- and meso-tetrakis(2-fluorophenyl)porphinatomanganese(II) (II), [MnTOMePP][TCNE] . 2PhMe, 1, and [MnTFPP][TCNE] . 2PhMe, 2, respectively, have een structurally and magnetically characterized. 1 and 2 belong to the triclinic Pi (No. 2) space group [1, a = 9.896(2) Angstrom, b = 10.256(3) Angstrom, c = 14.447(2) Angstrom, alpha = 82.64(2)degrees, beta = 92.40(1)degrees, gamma = 109.07(2)degrees, T = -80 degrees C, Z = 1, and R(F-0) = 0.0295; 2, a = 10.185(5) Angstrom, b = 11.081(3) Angstrom, c = 12.378(3) Angstrom, alpha = 107.55(2)degrees, beta = 82.88(3)degrees, gamma = 111.09(3)degrees, T = -80 degrees C, Z = 1, and R(F-0) = 0.0421]. 1 and 2 are coordination polymers with the Mn(III) sites bridged by trans-mu-sigma-[TCNE](.-). The [TCNE](.-) is orientationally disordered in 2, with the minor form being rotated by 90 degrees with respect to the major form and in the same plane as the major form in an approximate 5:1 ratio. The Mn-N and intrachain Mn Mn distances are 2.289 and 2.313 Angstrom and 10.256 and 10.185 Angstrom. and the Mn-N-C and the dihedral angle between the mean MnN4-porphyrin and the mean [TCNE](.-) planes are 165.53 and 78.1 degrees and 148.6 and 55.4 degrees for 1 and the occupancy-weighted average of 2, respectively. For 1 above 250 K the susceptibility can be fit by the Curie-Weiss expression with theta = -65 K, while between 75 and 190 K an effective theta of +21 K is observed; for 2 above 225 K, theta is -71 K, while between 40 and 100 K the effective theta is +45 K. The initial negative theta values along with minima in the T-chi(T) data at 134 K (X = OMe) and 240 K (X = F) are consistent with antiferromagnetic coupling. One (chi)"(T) and two (chi)'(T) peaks are observed for both 1 and 2. The higher temperature [similar to-10 K (1) and 12.5 K (2)] (chi)'(T) peaks are frequency independent, lack a corresponding (chi)"(T) absorption, and are assigned to a transition to an antiferromagnetic state. In contrast, the lower-temperature frequency dependent [5.6 K (1) and 7.5 K (2) at 10 Hz] (chi)'(T) peaks have a corresponding frequency dependent (chi)"(T) peaks and are assigned to the transition to a spin-glass or superparamagnetic state. The T-c's are defined as (chi)'(T) data taken at 10 Hz and are listed above.

  DOI：

  10.1021/ic9710768

文献信息

• Synthesis and Magnetic Exchange Properties of Linear Trinuclear Oxo-Bridged MIIIORuIVOMIII Complexes (M = Fe, Cr, Mn) Formed by Two-Electron Redox Reactions
  作者：Kevin J. Berry、Boujemaa Moubaraki、Keith S. Murray、Peter J. Nichols、Lewis D. Schulz、Bruce O. West

  DOI：10.1021/ic00120a017

  日期：1995.8

  The two-electron reductions of various porphyrin complexes Ru-VI(O)(2)(P) by Fe(II), Cr(II), and Mn(II) compounds of porphyrins and salicylaldimines result in the formation of heterotrimetallic ore-bridged complexes (L)M(III)-ORuIV(P)OM(III)(L) (M = Fe(III), Cr(III), Mn(III); P is the dianion of 5,10,15,20-tetraarylporphyrins, such as tetraphenylporphyrin (TPP), tetrakis(p-methoxyphenyl)porphyrin (TMP), or 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP); L is TPP, TMP, or OEP or the dianions of N,N'-(4-methyl-4-azaheptane-1,7-diyl)bis(salicylaldimine) (salmah) or N,N'-ethane-1,2-diylbis(salicylaldimine) (salen). A detailed study of the temperature- and field-dependent magnetic properties of this rather novel series of (L)M(III)ORu(IV)(P)OM(III)(L) compounds has been made. The spin-states of the constituent metal centers are as follows: Ru-IV, S-Ru = 1 (d(4)); Fe-III S-Fe = 5/2 (d(5)); Cr-III, S-Cr = 3/2 (d(3)); Mn-III, S-Mn = 4/2 (d(4)). The spin-state and coordination geometry of the (L)Fe-III groups were confirmed by Mossbauer spectral measurements. Trinuclear combinations of the present kind give rise to unusual coupled spin-state energy levels which, in the case of (L)(FeORuIV)-O-III(P)OFeIII(L) compounds, result in ''ferromagnetic-like'' plots of magnetic moment versus temperature, particularly at low temperatures. The following best-fit values of parameters were deduced from the magnetic moment data, obtained in 1 T fields over the temperature range 4.2-300 K. (salmah)FeORu(TPP)OFe(salmah): g = 1.97, J(12) = -19.7 cm(-1), J(13) = +6.5 cm(-1), alpha J(13)/J(12) = -0.33, ground-state S = 4; (TMP)FeORu(TPP)OFe(TMP): g = 1.95, J(12) = -23.4 cm(-1), J(13) = 5.4 cm(-1), alpha = -0.23, ground-state S = 4. (TPP)FeORu(TPP)OFe(TPP): g = 2.0, J(12) = -35.7 cm(-1), J(13) = 11.2 cm(-1), alpha = -0.31, ground-state S = 4, [(TPP)Fe]O-2 impurity = 13%, zero-field splitting of the S = 4 state (D cm approximate to 5 cm(-1)). (TMP)MnORu(TPP)OMn(TMP): g = 1.93, J(12) = -17.4 cm(-1), J(13) = 9.6 cm(-1), alpha = -0.55, groundstate S = 3. (TPP)CrORu(TPP)OCr(TPP): g = 1.98, J(12) = -25.3 cm(-1), J(13) = -11.1 cm(-1), alpha = 0.44, groundstate S = 1. Possible reasons for the small sizes of the J(12) values, in comparison to those of related M(III)OM(III) and (RuORuIV)-O-IV compounds, are discussed.