5,15-di(3,5-di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphin | 138253-31-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: 5,15-di(3,5-di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphin
• 英文别名: 5,15-Bis(3,5-di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin；5,15-bis(2,5-di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin；etioporphyrin
• CAS: 138253-31-3
• 化学式: C₆₀H₇₈N₄
• 分子量: 855.306
• InChiKey: SRDZSVPSKDMVRQ-JOTUAKGVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.26
• 重原子数：
  64.0
• 可旋转键数：
  6.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  57.36
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  5,15-di(3,5-di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphin 在 2,3,5-三甲基吡啶 、 iron(II) bromide 、 盐酸 作用下， 以 四氢呋喃 、 甲苯 、 二氯甲烷 为溶剂， 反应 1.0h， 以60%的产率得到iron(III) 5,15-bis(3,5-di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin chloride
  参考文献：
  名称：

  Enhanced Intersystem Crossing in Donor/Acceptor Systems Based on Zinc/Iron or Free-Base/Iron Porphyrins

  摘要：

  The deactivation pathways of the singlet excited state of a series of zinc or free-base donor porphyrins covalently linked by a bridge to a paramagnetic iron(III) chloride porphyrin acceptor have been studied. These donor-bridge-acceptor systems all share a similar geometry (25 Angstrom donor-acceptor center-to-center distance), but the bridges vary in electronic structure. In previously reported investigations of zinc/iron porphyrin systems, the fluorescence quenching of the donor has predominantly been assigned to electron transfer. However, for the porphyrin systems studied in this paper, we show that the dominant deactivation channels are enhanced intersystem crossing and singlet energy transfer. In both series, the intersystem crossing rate (S-1 --> T-1) of the donor moiety is almost doubled in the presence of a paramagnetic high-spin metal-porphyrin acceptor. The significant spectral overlap of the donor fluorescence and acceptor absorption in both series allows for efficient singlet energy transfer (Forster mechanism). Furthermore, the bridging chromophores mediate energy transfer and the enhancement is inversely dependent upon the energy gap between the donor and bridge excited states. Although Marcus theory predicts thermodynamically favorable electron transfer to occur in the systems investigated, the quenching rate constants were found to be independent of solvent polarity, and no charge-separated state could be detected, indicating very small electronic coupling for election transfer.

  DOI：

  10.1002/1521-3765(20010518)7:10<2122::aid-chem2122>3.0.co;2-n
• 作为产物：
  描述：

  4′-(4-甲基苯基)-2,2′:6′,2′′-三吡啶 在 盐酸 、 N-溴代丁二酰亚胺(NBS) 、 乌洛托品 、 三氟乙酸 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 17.0h， 生成 5,15-di(3,5-di-tert-butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphin
  参考文献：
  名称：

  刚性连接至一个或两个用于组装亚基的三联吡啶螯合物的卟啉

  摘要：

  （3,3'-二乙基-4,4'-二甲基-2,2'-二吡咯基）甲烷与带有2,2'，6'，2''-吡啶的芳族醛的“ 2 + 2”缩合（中间卟啉原氧化后，配体导致带有两个平行反几何布置的叔丁基螯合物的卟啉。如果在苯甲醛衍生物的存在下进行相同的反应，则还将获得单叔卟啉。

  DOI：

  10.1016/s0040-4039(00)79442-1

文献信息

• A rotaxane with two rigidly held porphyrins as stoppers
  作者：Jean-Claude Chambron、Val�rie Heitz、Jean-Pierre Sauvage

  DOI：10.1039/c39920001131

  日期：——

  A rotaxane with two rigidly held porphyrins as stoppers is synthesized by a copper(I)-based template strategy.

  通过基于铜（I）的模板策略，合成了一种以两个刚性固定的卟啉为封止剂的轮烷。
• Multistep Electron Transfer between Porphyrin Modules Assembled around a Ruthenium Center
  作者：Anthony Harriman、Fabrice Odobel、Jean-Pierre Sauvage

  DOI：10.1021/ja00142a012

  日期：1995.9

  devised for the construction of photoactive multicomponent arrays based on metal ion chelation whereby bisporphyrins have been assembled around a central ruthenium(II) bis(terpyridyl) complex. One of the terminal subunits is a gold (III) porphyrin while the second terminus is selected from a gold (III), zinc(II), or free-base porphyrin. Photophysical properties have been measured for each of the tripartitic

  已经设计了一种新的策略来构建基于金属离子螯合的光活性多组分阵列，其中双卟啉围绕中心钌（II）双（三联吡啶）络合物组装。末端亚基之一是金 (III) 卟啉，而第二个末端选自金 (III)、锌 (II) 或游离碱卟啉。已经使用超快瞬态吸收和发射光谱测量了每种三重化合物的光物理特性。激发进入中央钌 (II) 双（三联吡啶）复合物后，分子内三重态能量快速转移到附加的卟啉之一。直接激发到金 (III) 卟啉亚基会产生相应的三重激发态，该激发态对能量或电子转移过程没有反应。相比之下，激发到锌 (II) 或游离碱卟啉中会产生相应的激发单线态，将电子转移到相邻的钌 (II) 双（三联吡啶）络合物。二次电子转移到附加的金 (III) 卟啉与反向电子转移竞争，使得氧化还原当量分离约 30 A。原始基态系统通过相对缓慢的卟啉间电子转移恢复。已经评估了这些电子转移步骤中的每一个的能量学。51 个参考文献，10 个图，1
• Synthesis of Bis(phenylethynyl)arylene-Linked Diporphyrins Designed for Studies of Intramolecular Energy Transfer
  作者：Johan Kajanus

  DOI：10.1055/s-1999-3525

  日期：1999.7
• Synthesis of a 1,3,5-triporphyrinylbenzene
  作者：Atsuhiro Osuka、Ben Li Liu、Kazuhiro Maruyama

  DOI：10.1021/jo00065a024

  日期：1993.6
• Dimeric and Trimeric Supramolecular Systems Formed by Donor‒Acceptor Interactions of ZnII, MnIII, and SnIV Porphyrin Complexes
  作者：E. M. Kuvshinova、O. V. Gornukhina、A. S. Semeikin、O. A. Golubchikov

  DOI：10.1134/s1070363217120556

  日期：2017.12

  The paper presents the methods of synthesis of dimeric and trimeric compounds formed by donor-acceptor interactions of Zn-II, Mn-III, and Sn-IV porphyrin complexes. The structure of the porphyrin ensembles was determined by H-1 NMR spectroscopy. The extra coordination properties of the synthesized dimeric and trimeric supramolecular systems in relation to nitrogen-containing compounds were studied and the stability constants of the resulting porphyrin extra complexes were determined.