5-(4-cyanophenyl)-10,15,20-tris(3,5-di-tert-butylphenyl)porphyrin | 125586-00-7

• 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-(4-cyanophenyl)-10,15,20-tris(3,5-di-tert-butylphenyl)porphyrin
• 英文别名: 5-(4-cyanophenyl)-10,15,20-tri(3,5-di-tert-butylphenyl)porphiryn
• CAS: 125586-00-7
• 化学式: C₆₉H₇₇N₅
• 分子量: 976.404
• InChiKey: NDVVTRGGHMWGPX-SWPMMZLJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.98
• 重原子数：
  74.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  81.15
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  5-(4-cyanophenyl)-10,15,20-tris(3,5-di-tert-butylphenyl)porphyrin 在 nickel diacetate 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 24.0h， 以78%的产率得到
  参考文献：
  名称：

  超分子卟啉通过羧酸idi盐盐桥和快速的集合内激发能量转移而组装。

  摘要：

  锌和游离碱卟啉的定义明确的超分子组装体是通过形成idi盐羧酸盐桥而构建的。研究了一对一的供体-受体对和四对一的天线型组件。稳态和时间分辨荧光测量结果明确表明，在这些组件中发生了从锌卟啉络合物到游离碱卟啉的有效单线单重激发能量转移。实际上，在两种类型的组件中观察到的能量传输速率都比Forster机制所建议的要快得多，这暗示了分子间直键机制的参与。

  DOI：

  10.1002/chem.200400152
• 作为产物：
  描述：

  吡咯 、 3,5-双(叔丁基)苯甲醛 、 4-氰基苯甲醛 以 丙酸 为溶剂， 以5.5%的产率得到5-(4-cyanophenyl)-10,15,20-tris(3,5-di-tert-butylphenyl)porphyrin
  参考文献：
  名称：

  Energy and Electron Transfer in Synthetic Oligoproline-BridgedPorphyrin Donor–Acceptor Molecules

  摘要：

  合成了寡-l-脯氨酸桥接双（卟啉）化合物。在乙醇中，受保护的低聚卟啉可能会在低聚数≥4时形成相当稳定的螺旋构象。在乙醇中，分子内单子能量从 N 端的光激发锌卟啉分子转移到 C 端的无金属卟啉分子，其效率与从 C 端的锌卟啉分子转移到 N 端的无金属卟啉分子的效率相同。在乙醇中，分子中的锌（II）卟啉向铁（III）卟啉也发生了光诱导电子转移，这种转移与间隔物的方向以及能量转移无关。分子内电子转移效率随着锌卟啉和铁卟啉之间的距离而发生微弱变化，这表明电子应通过寡脯氨酸连接中的酰胺键移动。

  DOI：

  10.1246/bcsj.67.1863

文献信息

• Linkage Dependent Charge Separation and Charge Recombination in Porphyrin-Pyromellitimide-Fullerene Triads
  作者：Hiroshi Imahori、Koichi Tamaki、Yasuyuki Araki、Taku Hasobe、Osamu Ito、Akihisa Shimomura、Santi Kundu、Tadashi Okada、Yoshiteru Sakata、Shunichi Fukuzumi

  DOI：10.1021/jp014433f

  日期：2002.3.1

  A homolocous series of zincporphyrin (ZnP)-pyromellitimide (Im)-C-60 linked triads where the pyromellitimide (Im) moiety is incorporated as an intermediate acceptor between the above two chromophores with a linkage of different spacers, ZnP-Im-CH2-C-60, ZnP-IM-C-60, and ZnP-CH2-Im-C-60 as well as the reference dyads (ZnP-Im-CH2-ref, ZnP-Im-ref, and ZnP-CH2-Im-ref) have been prepared to investigate linkage dependence of photoinduced electron transfer (ET) and back ET to the ground state in the triads. Time-resolved transient absorption spectra of the triads measured by picosecond laser photolysis as well as the fluorescence lifetimes in THF reveal the occurrence of photoinduced ET from the singlet excited state of the ZnP to the Im moiety to give the initial charge-separated state, i.e., the zincporphyrin radical cation (ZnP.+)-imide radical anion (Im(.-)) pair, followed by a charge shift (CSH) to produce the final charge-separated state, the ZnP.+-C-60(.-) pair. The rate constants of photoinduced ETs in ZnP-Im-C-60 (1.8 x 10(10) s(-1)) and ZnP-Im-CH2-C-60 (1.3 x 10(10) s(-1)) in THF are much larger than those in ZnP-CH2-IM-C-60 (2.9 x 10(9) s(-1)) and ZnP-CH2-Im-ref (1.9 x 10(9)) s-1). The larger charge separation (CS) rates in the former case are ascribed to the relatively strong electronic coupling because of the absence of a methylene linkage between the ZnP and the Im moieties in ZnP-Im-C-60 and ZnP-Im-CH2-C60 as compared to the triad and dyad with the methylene linkage. The transient absorption spectra of the final charge-separated state, the ZnP.+-C-60(.-) pair, have been also measured by nanosecond laser photolysis. It has been found that the rate constants of charge recombination (CR) of ZnP.+-Im-C-60(.-) are temperature independent, but that the CR rate constants of ZnP.+-Im-CH2-C-60(.-) exhibit an Arrhenius-like temperature dependence with an activation energy of 0.13 eV which corresponds to the energy difference between ZnP.+-Im(.-)CH(2)-C-60 and ZnP.+-Im-CH2-C-60(.-). This indicates that the relatively strong electronic coupling without methylene linkage in ZnP-IM-C60 results in the preference of the tunneling superexchange ET over the sequential ET in the CR process which requires the thermal activation to reach the higher energy state (i.e., ZnP.+-Im(.-)-C-60), whereas the sequential ET predominates in the triads with the methylene linkage.
• Zhilina, Z. I.; Ishkov, Yu. V.; Grushevaya, Zh. V., Doklady Chemistry, 1989, vol. 308, # 1-3, p. 254 - 258
  作者：Zhilina, Z. I.、Ishkov, Yu. V.、Grushevaya, Zh. V.、Andronati, S. A.

  DOI：——

  日期：——
• Ishkov, Yu. V.; Zhilina, Z. I.; Grushevaya, Zh. V., Journal of Organic Chemistry USSR (English Translation), 1990, vol. 26, # 11, p. 2101 - 2106
  作者：Ishkov, Yu. V.、Zhilina, Z. I.、Grushevaya, Zh. V.、Voloshanovskii, I. S.

  DOI：——

  日期：——
• ISHKOV, YU. V.;ZHILINA, Z. I.;GRUSHEVAYA, ZH. V.;VOLOSHANOVSKIJ, I. S., ZH. ORGAN. XIMII, 26,(1990) N1, S. 2433-2440
  作者：ISHKOV, YU. V.、ZHILINA, Z. I.、GRUSHEVAYA, ZH. V.、VOLOSHANOVSKIJ, I. S.

  DOI：——

  日期：——
• ISHKOV, YU. V.;GRUSHEVAYA, ZH. V., MATER. NAUCH. KONF. MOL. UCHENYX XIM. FAK. ODES. YH-TA, ODESSA, 22-23 CEH+
  作者：ISHKOV, YU. V.、GRUSHEVAYA, ZH. V.

  DOI：——

  日期：——