trans-[CrF2(1,4,8,10-tetraazabicyclo[10.2.2]hexadecane)][ClO4] | 935658-84-7

• 英文名称: trans-[CrF2(1,4,8,10-tetraazabicyclo[10.2.2]hexadecane)][ClO4]
• 英文别名: trans-[CrF2(1,4-C2-cyclam)][ClO4]
• CAS: 935658-84-7
• 化学式: C₁₂H₂₆CrF₂N₄*ClO₄
• 分子量: 415.809
• InChiKey: LCLNZQDAZAKJSA-UHFFFAOYSA-K

计算性质

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

反应信息

• 作为反应物：
  描述：

  trans-[CrF2(1,4,8,10-tetraazabicyclo[10.2.2]hexadecane)][ClO4] 、 重水 以 重水 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  Effects of steric constraint on chromium(III) complexes of tetraazamacrocycles, 4: Comparison of the trans-difluoro-complexes of tet a, 1,4-C2-cyclam, and 1,11-C3-cyclam

  摘要：

  The synthesis and characterization of the trans-difluorochromium(III) complexes of the constrained macrocyclic ligands 1,4-C-2-cyclam = 1,4,8,1 1-tetraazabicyclo[10.2.2]hexadecane and 1,11-C-3-cyclam = 1,4,8,11-tetraazabicyclo[9.3.3]heptadecane is reported. Only trans complexes are formed, and the structures of both trans-[Cr(1,4-C-2-cyclam)F-2]ClO4 and trans-[Cr(1,11-C-3-cyclam)F-2]CIO4 are presented. The photochemical and photophysical behavior of the 1,4-C-2-cyclam and 1, 11-C-3-cyclam complexes is compared with that of the corresponding tet a (C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) complex. The constraint imposed by the additional bridging groups of 1,4-C-2-cyclam and 1, 11-C-3-cyclam distorts the complexes away from both octahedral symmetry and centrosymmetry, as evidenced by the bond angles that deviate from ideal 90 degrees and 180 degrees values and by a significant distortion of the Cr(N-4) plane. This reduction in symmetry correlates with a monotonic increase in the extinction coefficients in going from the tet a to the 1, 11-C-3-cyclam, to the 1,4-C-2-cyclam complex. These three complexes also exhibit large variations in their aqueous room-temperature excited state behavior; namely, the lifetimes of the T-2(1g) (Oh) excited states are 30,60, and 1.0 mu s for the tet a, 1,11-C-3-cyclam, and 1,4-C-2-cyclam complexes, respectively. Studies of the excited-state lifetime of these complexes in acidified H2O/dimethyl sulfoxide over the temperature range between -30 and +95 degrees C suggest that the 1,4-C-2-cyclarn complex accesses a temperature-dependent relaxation mechanism at significantly lower temperatures than do the tet a or 1, 11-C-3-cyclam complexes. The emission behavior of these complexes is also solvent-dependent, consistent with established theories that the degree of splitting of the emitting T-2(1g) (Oh) state varies with the hydroxylic nature of the solvent. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2006.08.037
• 作为产物：
  描述：

  trans-[CrF2(py)4]ClO4 、 1,5,8,12-tetraazabicyclo<10.2.2>hexadecane 以 乙二醇甲醚 为溶剂， 以51%的产率得到trans-[CrF2(1,4,8,10-tetraazabicyclo[10.2.2]hexadecane)][ClO4]
  参考文献：
  名称：

  Effects of steric constraint on chromium(III) complexes of tetraazamacrocycles, 4: Comparison of the trans-difluoro-complexes of tet a, 1,4-C2-cyclam, and 1,11-C3-cyclam

  摘要：

  The synthesis and characterization of the trans-difluorochromium(III) complexes of the constrained macrocyclic ligands 1,4-C-2-cyclam = 1,4,8,1 1-tetraazabicyclo[10.2.2]hexadecane and 1,11-C-3-cyclam = 1,4,8,11-tetraazabicyclo[9.3.3]heptadecane is reported. Only trans complexes are formed, and the structures of both trans-[Cr(1,4-C-2-cyclam)F-2]ClO4 and trans-[Cr(1,11-C-3-cyclam)F-2]CIO4 are presented. The photochemical and photophysical behavior of the 1,4-C-2-cyclam and 1, 11-C-3-cyclam complexes is compared with that of the corresponding tet a (C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) complex. The constraint imposed by the additional bridging groups of 1,4-C-2-cyclam and 1, 11-C-3-cyclam distorts the complexes away from both octahedral symmetry and centrosymmetry, as evidenced by the bond angles that deviate from ideal 90 degrees and 180 degrees values and by a significant distortion of the Cr(N-4) plane. This reduction in symmetry correlates with a monotonic increase in the extinction coefficients in going from the tet a to the 1, 11-C-3-cyclam, to the 1,4-C-2-cyclam complex. These three complexes also exhibit large variations in their aqueous room-temperature excited state behavior; namely, the lifetimes of the T-2(1g) (Oh) excited states are 30,60, and 1.0 mu s for the tet a, 1,11-C-3-cyclam, and 1,4-C-2-cyclam complexes, respectively. Studies of the excited-state lifetime of these complexes in acidified H2O/dimethyl sulfoxide over the temperature range between -30 and +95 degrees C suggest that the 1,4-C-2-cyclarn complex accesses a temperature-dependent relaxation mechanism at significantly lower temperatures than do the tet a or 1, 11-C-3-cyclam complexes. The emission behavior of these complexes is also solvent-dependent, consistent with established theories that the degree of splitting of the emitting T-2(1g) (Oh) state varies with the hydroxylic nature of the solvent. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2006.08.037