fac-trichloro(1,4,7-triazacyclononane)rhodium(III) | 72953-98-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: fac-trichloro(1,4,7-triazacyclononane)rhodium(III)
• 英文别名: [Rh(III)(tacn)Cl3]；[Rh(III)(1,4,7-triazacyclononane)Cl3]；1,4,7-triazonane;trichlororhodium
• CAS: 72953-98-1
• 化学式: C₆H₁₅Cl₃N₃Rh
• 分子量: 338.47
• InChiKey: KCVGRGNRXBURIL-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：

  fac-trichloro(1,4,7-triazacyclononane)rhodium(III) 在 silver perchlorate HClO₄ 作用下， 以 高氯酸 为溶剂， 以50%的产率得到Di-μ-hydroxo-bis[hydroxo(1,4,7-triazacyclononan)rhodium(III)]-diperchlorat*4H2O
  参考文献：
  名称：

  Wieghardt, Karl; Schmidt, Wilfried; Nuber, Bernhard, Chemische Berichte, 1980, vol. 113, # 1, p. 36 - 41

  摘要：

  DOI：
• 作为产物：
  描述：

  氯化铑(三水) 、 1,4,7-三氮杂环壬烷 以 甲醇 为溶剂， 以51%的产率得到fac-trichloro(1,4,7-triazacyclononane)rhodium(III)
  参考文献：
  名称：

  配体大环对铑（III）配合物的光物理性质的影响：顺式和反式二氰基（1,4,8,11-四氮杂环十四烷）铑（III）及其相关物种的详细研究

  摘要：

  Described are photophysical properties for the dicyano tetrazamacrocycle Rh(III) complexes trans- and cis-Rh([14]aneN4)(CN)2+ and trans-Rh([15]aneN4)(CN)2+ (I, IV, and II, respectively, [14]aneN4 = 1,4,8,11-tetraazacyclotetradecane, [15]aneN4 = 1,4,8,12-tetraazacyclopentadecane) plus related compounds. The electronic absorption spectra of the complexes are characterized by broad bands with lambda(max) in the near-ultraviolet region (epsilon < 300 M-1 cm-1) assigned as spin-allowed ligand field (LF) transitions. Emission spectra are characterized by broad. unstructured, visible range bands assigned as spin-forbidden transitions from the lowest energy 3LF states. A Franck-Condon analysis of the emission spectrum based on a two acceptor mode model was performed, and the results were consistent with average bond displacements in the excited state of ca. 0. 14 angstrom for a Rh-N bond and 0.02 angstrom for the N-H bonds. Both I and II luminesce strongly in ambient temperature aqueous solutions, but the measured lifetime (tau(m)) of the former proved to be an order of magnitude longer. The tau(m) values were measured over the mange 77-300 K, and lifetimes of both I and II exhibited temperature-independent (at lower T) and temperature-activated regions. Notably, the activation energy for nonradiative decay (k(n)) of the 3LF state of I is significantly larger than that observed for II At 77 K, values of tau(m) for the various complexes were found to correlate with the estimated nu-00 of the bands, and the isotope effect on the nonradiative mte resulting from D/H exchanging the amine protons was shown to increase with the number of N-H bonds in the complex. Molecular mechanics calculations were also carried out to probe the potential effects of ligand field excitation on the total strain energy of these tetraazamacrocycle complexes resulting from the connectivity between the amine nitrogens. These photophysical properties are discussed in terms of competitive weak and strong coupling mechanisms for nonradiative deactivation.

  DOI：

  10.1021/j100195a024

文献信息

• Synthesis and crystal structures of water-soluble rhodium(III) complexes with 1,4,7-triazacyclononane and 2,2′-bipyridine supporting ligands
  作者：Hideki Hayashi、Hiromi Nishida、Seiji Ogo、Shunichi Fukuzumi

  DOI：10.1016/j.ica.2004.03.001

  日期：2004.7

  New water-soluble rhodium(III) complexes with a tacn (1,4,7-triazacyclononane) and a bpy (2,2′-bipyridine) supporting ligands were synthesized. The reaction of [RhIII(tacn)Cl3] (1) with equimolar amount of bpy and two equivalents of AgNO3 in H2O at reflux for 10 h gave a water-soluble chloro complex [RhIII(tacn)(bpy)Cl](NO3)2 2(NO3)2}. Complex 2(NO3)2 was treated with equimolar amount of AgNO3 in

  用TACN（1,4,7-三氮杂环）和联吡啶（2,2-新水溶性铑（III）络合物'支承的配体联吡啶）的合成。[Rh III（TAcn）Cl 3 ]（1）与等摩尔量的bpy和两当量的AgNO 3在H 2 O中的反应在回流下反应10 h，得到水溶性氯络合物[Rh III（TAcn）（bpy） ）Cl]（NO 3）2 2（NO 3）2 }。复杂2（NO 3）2用的硝酸银等摩尔量治疗3 H中2O在回流下10小时，得到水溶性硝酸根络合物[Rh III（TAcn）（bpy）（NO 3）]（NO 3）2 3（NO 3）2 }。的水溶解度3与NO 3  -配位体（46.5毫克/毫升）中的高与比较2有Cl -配体（14.5毫克/毫升）相同的条件下（在pH 7.0在25℃）。X射线分析明确确定了2和3的结构。他们在H 2 O中的结构也用11 H NMR，IR和电喷雾电离质谱（ESI-MS）。