[trans-Rh(1,4,8,12-tetraazacyclopentadecane)Cl2]Cl | 142762-39-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [trans-Rh(1,4,8,12-tetraazacyclopentadecane)Cl2]Cl
• 英文别名: trans-dichloro(1,4,8,12-tetraazacyclopentadecane)rhodium(III) chloride
• CAS: 142762-39-8；251323-63-4
• 化学式: C₁₁H₂₆Cl₂N₄Rh*Cl
• 分子量: 423.619
• InChiKey: BLZRWORFVWABGA-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-Rh(1,4,8,12-tetraazacyclopentadecane)Cl2]Cl 在 三氟甲磺酸 、 氨 作用下， 以33%的产率得到trans-dichloro(1,4,8,12-tetraazacyclopentadecane)rhodium(III) perchlorate
  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
• 作为产物：
  描述：

  1,4,8,12-四氮杂环十五烷 、 氯化铑(三水) 以 甲醇 为溶剂， 以73%的产率得到[trans-Rh(1,4,8,12-tetraazacyclopentadecane)Cl2]Cl
  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

• Ground-State, Mode-Dependent Vibronic Coupling in Some Simple, Cyanide-Bridged Transition-Metal Donor−Acceptor Complexes
  作者：Ariel V. Macatangay、Selma Elaine Mazzetto、John F. Endicott

  DOI：10.1021/ic9904743

  日期：1999.11.1

  Patterns of the shifts in bridging cyanide-stretching frequencies have been examined in several fully saturated, mu-cyano, bi- or trimetallic transition-metal donor-acceptor (D/A) complexes. An earlier (Watzky, M. A.; et al. Inorg. Chem. 1996, 35, 3463) inference that the bridging ligand nuclear and the D/A electronic coordinates are entangled is unequivocally demonstrated by the 32 cm(-1) lower frequency of v(CN) for (NH3)(5)Cr(CNRu(NH3)(5))(4+) than for the cyanopentaamminechromium(III) parent. This contrasts to the 41 cm(-1) increase in v(CN) upon ruthenation of (NH3)(5)RhCN2+. More complex behavior has been found for cis and trans trimetallic, donor-acceptor complexes. The symmetric combination of CN- stretching frequencies in trans-Cr-III(MCL)(CNRuII(NH3)(5))(2)(5+) complexes (MCL = a tetraazamacrocyclic ligand) shifts 100-140 cm(-1) to lower frequency, and the antisymmetric combination shifts less than about 30 cm(-1). This contrast in the shifts of the symmetric and the antisymmetric combinations of the CN stretches persists even in a trans complex with no center of symmetry. Two CN stretches have also been resolved in an analogous cis complex, and both shift to lower frequency by about 60 cm(-1). The net shift, summed over all the CN-stretching frequencies, is about the same for the bis-ruthenates of related dicyano complexes. A simple, symmetry-adapted perturbation theory treatment of the coupled vibrations is employed to deal with the opposing effects of the "kinematic" shifts (delta) of v(CN) to higher frequency, expected in the absence of D/A coupling, and shifts (f) of v(CN) to lower frequency that occur when D/A coupling is large. The Rh(III)and Cr(III)-centered complexes correspond to different limits of this model: delta > f and delta < f, respectively. When referenced by means of this model to complexes with Rh(III) acceptors, the shifts in trimetallic complexes, summed over the symmetric and antisymmetric combinations of CN stretches, are about twice those of bimetallic complexes. Similarly referenced and summed over all bridging CN frequencies, the shifts of v(CN) to lower energies are proportional to the oscillator strength of the electronic, donor-acceptor charge-transfer transition. The simplest interpretation of this correlation is that the donor-acceptor coupling in these systems is a function of the nuclear coordinates of the bridging ligand. This behavior of these complexes is semiquantitatively consistent with expectation for CN--mediated vibronic (pseudo-Jahn-Teller) coupling of neighboring donors and accepters, and the observed Ru-II/CN- CT absorption parameters can be used in a simple, semiclassical vibronic model to predict shifts in v(CN) that are in reasonable agreement with those observed.