1,4,8,11-tetraazabicyclo[9.3.3]heptadecane | 246861-30-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,4,8,11-tetraazabicyclo[9.3.3]heptadecane
• 英文别名: 1,11-C3-Cyclam；1,4,8,11-Tetrazabicyclo[9.3.3]heptadecane；1,4,8,11-tetrazabicyclo[9.3.3]heptadecane
• CAS: 246861-30-3
• 化学式: C₁₃H₂₈N₄
• 分子量: 240.392
• InChiKey: ZGMXPFPPISTDFN-UHFFFAOYSA-N

物化性质

• 沸点：
  361.3±10.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  30.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-[CrF2(py)4]ClO4 、 1,4,8,11-tetraazabicyclo[9.3.3]heptadecane 以 乙二醇甲醚 为溶剂， 以43%的产率得到trans-[CrF2(1,4,8,11-tetraazabicyclo[9.3.3]heptadecane)][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

文献信息

• Solution-State and Solid-State Structural Characterization of Complexes of a New Macrocyclic Ligand Containing the 1,5-Diazacyclooctane Subunit
  作者：Chuanjiang Hu、Thoi D. Nguyen、Paul S. Wagenknecht、Lawrence C. Nathan

  DOI：10.1021/ic020495o

  日期：2003.2.1

  been characterized by single-crystal X-ray crystallography. For the Ni(II) complex, the 1,5-diazacyclooctane (daco) subunit of the ligand is in the chair-boat conformation, whereas that same subunit in the Co(III) complex is in the chair-chair conformation. For the Ni(II) complex, C(12) and H(12a) block one of the coordination sites. The (1)H and (13)C NMR spectra of the Ni(II) complex in D(2)O have very

  合成和表征的一种新的约束四氮杂大环配体，1,4,8,11-四氮杂双环[9.3.3]十七烷（1,11-C（3）-cyclam）。由于其碱性，该配体（质子化形式的pK（a）> 13.5）需要非质子溶剂进行金属化反应。此配体的两个复合物，[Ni（1,11-C（3）-cyclam]（OTf）（2）和[Co（1,11-C（3）-cyclam）（NCS）（2）]（OTf ），已通过单晶X射线晶体学表征了。对于Ni（II）配合物，配体的1,5-二氮杂环辛烷（daco）亚基处于椅形结构，而Co中的相同亚基（III）的配合物呈椅-椅构型，对于Ni（II）的配合物，C（12）和H（12a）阻断了其中一个配位点，该化合物的（1）H和（13）C NMR光谱D（2）O中的Ni（II）络合物具有非常尖锐的共振，表明低旋转Ni（II）。H（12a）的共振出现在4.5 ppm处，表明与Ni（II）有相互作用。在乙腈中，（
• Effects of Steric Constraint on Chromium(III) Complexes of Tetraazamacrocycles, 2. Comparison of the Chemistry and Photobehavior of the <i>trans</i>-Dichloro- and <i>trans-</i>Dicyano- Complexes of Cyclam, 1,4-C₂-Cyclam, and 1,11-C₃-Cyclam
  作者：Paul S. Wagenknecht、Chuanjiang Hu、Denise Ferguson、Lawrence C. Nathan、Robert D. Hancock、Jason R. Whitehead、Kimberley Wright-Garcia、Michael T. Vagnini

  DOI：10.1021/ic051366l

  日期：2005.12.1

  The synthesis and characterization of several Cr(III) complexes of the constrained macrocyclic ligand 1,11-CY cyclam (1,4,8,11-tetraazabicyclo[9.3.3]heptadecane)is reported. Only trans complexes are formed, and the structure of trans-[Cr(1,1 1-C-3-cyclam)Cl-2]PF6 is presented. The chemical and photophysical behavior of the 1,11-C-3-cyclam complexes are compared with those of the corresponding cyclarn (1,4,8,11 tetraazacyclotetradecane) and 1,4-C(2-)cyclam (1,4,8,11-tetraazabicyclo[10.2.2)hexadecane) complexes. The aquation rate of trans-[Cr(1,11-C-3-cyclam)Cl-2](+) is similar to that of the corresponding 1,4-C-2-cyClam complex and is more than 5 orders of magnitude faster than the cyclam counterpart. A monotonic increase in the extinction coefficient is observed on going from the cyclam complexes to the 1,11-C(3-)cyclam complexes to the 1,4-C-2-cyclam complexes, and this is related to the degree of centrosymmetry in each complex. The trans- [Cr(1, 11-C-3-cyclam) (CN)(2)](+) complex is a weak emitter in aqueous solution with a room-temperature emission maximum at 724 nm (tau = 23 mu s). Like the corresponding 1,4-C-2-cyclam complex (tau = 0.24 mu s), the 1,11-C-3-cyclam complex shows no deuterium-isotope effect in room-temperature solution. This is in marked contrast to the corresponding cyclam complex which has an emission lifetime of 335 mu s and a significant deuterium isotope effect in room-temperature solution. Low temperature (77K) data are also presented in an attempt to understand the differences in photophysical behavior.
• 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
  作者：Michael T. Vagnini、W. Caleb Rutledge、Chuanjiang Hu、Donald G. VanDerveer、Paul S. Wagenknecht

  DOI：10.1016/j.ica.2006.08.037

  日期：2007.4

  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.