4-ethynyl-1-[[zinc(II) porphyrinyl]phenylethynyl]bicyclo[2.2.2]-octane | 307334-83-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 4-ethynyl-1-[[zinc(II) porphyrinyl]phenylethynyl]bicyclo[2.2.2]-octane
• CAS: 307334-83-4
• 化学式: C₆₄H₇₂N₄Zn
• 分子量: 962.692
• InChiKey: WSSDAMBLBKKSFE-DKUKCONFSA-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：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  4-ethynyl-1-[[zinc(II) porphyrinyl]phenylethynyl]bicyclo[2.2.2]-octane 、 5-(3,5-Di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-15-iodophenylporphyrin 在 catalyst: Pd₂dba3*CHCl₃ 、 As(C₆H₅)3 作用下， 以 甲苯 为溶剂， 以40%的产率得到4-[5-[(3,5-di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-15-porphyrinyl]-phenylethynyl]-1-[[zinc(II)-5-(3,5-di-tert-butylpheny)-2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-15-porphyrinyl]phenylethynyl]bicyclo[2.2.2]-octane
  参考文献：
  名称：

  Mediated Electronic Coupling:  Singlet Energy Transfer in Porphyrin Dimers Enhanced by the Bridging Chromophore

  摘要：

  We have studied singlet electronic energy transfer (EET) in two donor-bridge-acceptor series (D-B -A), in which the donor (zinc porphyrin or its pyridine complex) and the acceptor (free base porphyrin) were covalently connected by a geometrically well-defined bridging chromophore. We have investigated how the medium between a donor and an acceptor influences EET by separating the influence of the electronic structure of the bridging chromophore from other effects known to influence the energy transfer. The electronic structure of the bridging chromophore was varied by changing the central unit (bicyclo[2.2.2]octane, benzene, naphthalene, or anthracene) in the bridging chromophore. In all systems the excited state energy separation donor-bridge and bridge-acceptor is large enough to prevent stepwise singlet energy transfer. In addition, the systems were designed to minimize conjugation to preserve the identity of the separate chromophores (donor, bridge, acceptor). Compared with the rate constant expected from the Forster theory, the bridging chromophore with bicyclo[2.2.2]octane as the central unit did not significantly enhance the energy transfer rate constant. However, the bridging chromophores with benzene and naphthalene as the central unit showed a moderate increase, whereas the bridging chromophore with anthracene as the central unit showed the largest increase in energy transfer rate constant. This increase is ascribed to a mediating effect of the bridging chromophore and it is proposed to be strongly correlated to the energy splitting between the singlet excited states of donor and bridging chromophores.

  DOI：

  10.1021/jp9909098
• 作为产物：
  描述：

  4-[(triisopropylsilyl)ethynyl]-1-[[zinc(II)5-(3,5-di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-15-porphyrinyl]phenylethynyl]bicyclo[2.2.2]-octane 在 四丁基氟化铵 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 以86%的产率得到4-ethynyl-1-[[zinc(II) porphyrinyl]phenylethynyl]bicyclo[2.2.2]-octane
  参考文献：
  名称：

  Mediated Electronic Coupling:  Singlet Energy Transfer in Porphyrin Dimers Enhanced by the Bridging Chromophore

  摘要：

  We have studied singlet electronic energy transfer (EET) in two donor-bridge-acceptor series (D-B -A), in which the donor (zinc porphyrin or its pyridine complex) and the acceptor (free base porphyrin) were covalently connected by a geometrically well-defined bridging chromophore. We have investigated how the medium between a donor and an acceptor influences EET by separating the influence of the electronic structure of the bridging chromophore from other effects known to influence the energy transfer. The electronic structure of the bridging chromophore was varied by changing the central unit (bicyclo[2.2.2]octane, benzene, naphthalene, or anthracene) in the bridging chromophore. In all systems the excited state energy separation donor-bridge and bridge-acceptor is large enough to prevent stepwise singlet energy transfer. In addition, the systems were designed to minimize conjugation to preserve the identity of the separate chromophores (donor, bridge, acceptor). Compared with the rate constant expected from the Forster theory, the bridging chromophore with bicyclo[2.2.2]octane as the central unit did not significantly enhance the energy transfer rate constant. However, the bridging chromophores with benzene and naphthalene as the central unit showed a moderate increase, whereas the bridging chromophore with anthracene as the central unit showed the largest increase in energy transfer rate constant. This increase is ascribed to a mediating effect of the bridging chromophore and it is proposed to be strongly correlated to the energy splitting between the singlet excited states of donor and bridging chromophores.

  DOI：

  10.1021/jp9909098

文献信息

• Bridge-Dependent Electron Transfer in Porphyrin-Based Donor−Bridge−Acceptor Systems
  作者：Kristine Kilså、Johan Kajanus、Alisdair N. Macpherson、Jerker Mårtensson、Bo Albinsson

  DOI：10.1021/ja003820k

  日期：2001.4.1

  Photoinduced electron transfer in donor-bridge-acceptor systems with zinc porphyrin (or its pyridine complex) as the donor and gold(III) porphyrin as the acceptor has been studied. The porphyrin moieties were covalently linked with geometrically similar bridging chromophores which vary only in electronic structure. Three of the bridges are fully conjugated pi-systems and in a fourth, the conjugation

  已经研究了以锌卟啉（或其吡啶配合物）为供体和金（III）卟啉作为受体的供体-桥-受体系统中的光致电子转移。卟啉部分与几何上相似的桥接发色团共价连接，这些发色团仅在电子结构上有所不同。其中三个桥是完全共轭的 pi 系统，在第四个中，共轭被破坏。对于具有此桥的系统，供体的单线态激发态的淬灭速率与溶剂无关，并且对应于 Förster 机制预期的单线态能量转移速率。相比之下，具有 pi 共轭桥接发色团的系统显示出依赖于溶剂的淬灭速率，表明在 Marcus 正常区域中存在电子转移。这得到了皮秒瞬态吸收测量的支持，这表明锌卟啉自由基阳离子仅在具有 pi 共轭桥接发色团的系统中形成。根据 Marcus 和 Rehm-Weller 方程，估计这些系统的供体和受体之间的电子耦合为 5-20 cm(-)(1)。对于在施主和桥单重激发态之间具有最小能隙的系统，发现了最大的耦合。这与使用量子力学方法计算的耦合非常