7-(1,2-dihydro-1,2-methanofullerene[60]-61-carbonyl)-9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene | 887951-52-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 7-(1,2-dihydro-1,2-methanofullerene[60]-61-carbonyl)-9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene
• CAS: 887951-52-2
• 化学式: C₁₀₅H₅₅NO
• 分子量: 1346.6
• InChiKey: LQNIQBJQVDNYCZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  28.5
• 重原子数：
  107
• 可旋转键数：
  15
• 环数：
  38.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  7-(1,2-dihydro-1,2-methanofullerene[60]-61-carbonyl)-9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene 、 丙二腈 在 吡啶 、 四氯化钛 作用下， 以 甲苯 为溶剂， 反应 0.08h， 生成
  参考文献：
  名称：

  Synthesis and characterization of highly photoresponsive fullerenyl dyads with a close chromophore antenna–C60 contact and effective photodynamic potential

  摘要：

  我们报告了一类新型光致伸缩性 C60âDCEâ 二苯胺芴纳米结构的合成及其分子内光诱导的能量和电子转移现象。通过化学方法将 C60(>DPAF-Cn) 中的酮基转化为电子吸附性更强的 1,1-二氰基乙烯（DCE）单元，对其进行了结构改造，从而得到了电子极化程度更高的 C60(>CPAF-Cn)。这种改性还导致可见光谱中的主要波段发生了很大的浴色偏移，使吸收波长达到 600 纳米，并将 C60âDCEâDPAF 纳米结构的光致发光能力扩展到比 C60(>DPAF-Cn) 更长的红色波长。因此，C60(>DPAF-Cn) 可以使用 1000â1200 nm 的光波长进行 2γ-PDT 以增强组织穿透深度。研究发现，密切相关的 C60(>DPAF-C2M) 产生单线态氧的效率与四苯基卟啉光敏剂相当。值得注意的是，C60(>CPAF-C2M) 的单线态氧量子产率比 C60(>DPAF-C2M) 高出近 6 倍，这表明 CPAF-C2M 分子的光收集能力大大增强，并导致 C60> 笼分子产生更高效的三重态。这导致 C60(>CPAF-C2M) 通过光动力疗法（200 J cmâ2 白光）高效杀死 HeLa 细胞。我们认为，与酮基相比，1,1-二氰基乙烯基具有扩展的Ï-共轭作用和更强的电子吸收能力。

  DOI：

  10.1039/c0jm00037j
• 作为产物：
  描述：

  7-α-bromoacetyl-9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene 、 足球烯 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以68%的产率得到7-(1,2-dihydro-1,2-methanofullerene[60]-61-carbonyl)-9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene
  参考文献：
  名称：

  Large concentration-dependent nonlinear optical responses of starburst diphenylaminofluorenocarbonyl methano[60]fullerene pentads

  摘要：

  PAF-C9，C60(>D�-DPAF)2，C60(>DPAF-C9)4，C60(>DPAF-C9)22，C60(>DPAF-C9)42，C60(>DPAF-C9)43，C60(>DPAF-C9)44，C60(>DPAF-C9)45，C60(>DPAF-C9)46，C60(>DPAF-C9)47，C60(>DPAF-C9)48，C60(>DPAF-C9)49，C60(>DPAF-C9)50，C60(>DPAF-C9)51，C60(>DPAF-C9)52，C60(>DPAF-C9)53，C60(>DPAF-C9)54，C60(>DPAF-C9)55，C60(>DPAF-C9)56，C60(>DPAF-C9)57，C60(>DPAF-C9

  DOI：

  10.1039/b615697e

文献信息

• Large concentration-dependent nonlinear optical responses of starburst diphenylaminofluorenocarbonyl methano[60]fullerene pentads
  作者：Hendry I. Elim、Robinson Anandakathir、Rachel Jakubiak、Long Y. Chiang、Wei Ji、Loon-Seng Tan

  DOI：10.1039/b615697e

  日期：——

  We demonstrate an approach toward the design of starburst C60-keto-DPAF assembly by applying a starburst macromolecular configuration with C60 as the core center, which is encapsulated by multiple bulky groups leading to the increase of intermolecular separation and aggregation barrier. Molecular compositions of the resulting C60(>DPAF-C9)2 triad and C60(>DPAF-C9)4 pentads were clearly confirmed by MALDI-MS (positive ion) detection of protonated molecular mass ions. Both C60(>DPAF-C9)22 and C60(>DPAF-C9)4 (structural isomers, 3a and 3b) exhibited nonlinear optical transmittance reduction responses in the femtosecond (fs) region with a lower transmittance value for the latter at the high laser power above 80 GW cm−2. This was attributed to the larger fs 2PA cross-section values of 3a and 3b than that of 2 at the same concentration and, apparently, correlated to a higher number of DPAF-C9 subunits in the structure of 3. As the concentration was decreased to 10−4 M, a clear monotonous increase of the σ2 value change (Δσ2) from 13.9, 33.2, to 48.1 and 68.2 × 10−48 cm4 s photon−1 molecule−1 (or 6820 GM for the latter) for the structural variation from the monoadduct 1, bisadduct 2, to tetraadducts 3b and 3a, respectively, was observed. We interpreted the concentration-dependent phenomenon as being due to the high tendency of fullerene-DPAF chromophores to form nanoscale aggregates at concentrations above 10−3 M. We also proposed that starburst structures, as exemplified by C60(>DPAF-C9)4, in a multipolar arrangement resembling encapsulation of C60 by DPAF-C9 pendants, provide a useful means to increase the degree of molecular dispersion and maintain high nonlinear optical efficiency.

  PAF-C9，C60(>D�-DPAF)2，C60(>DPAF-C9)4，C60(>DPAF-C9)22，C60(>DPAF-C9)42，C60(>DPAF-C9)43，C60(>DPAF-C9)44，C60(>DPAF-C9)45，C60(>DPAF-C9)46，C60(>DPAF-C9)47，C60(>DPAF-C9)48，C60(>DPAF-C9)49，C60(>DPAF-C9)50，C60(>DPAF-C9)51，C60(>DPAF-C9)52，C60(>DPAF-C9)53，C60(>DPAF-C9)54，C60(>DPAF-C9)55，C60(>DPAF-C9)56，C60(>DPAF-C9)57，C60(>DPAF-C9
• Synthesis and characterization of highly photoresponsive fullerenyl dyads with a close chromophore antenna–C60 contact and effective photodynamic potential
  作者：Long Y. Chiang、Prashant A. Padmawar、Joy E. Rogers-Haley、Grace So、Taizoon Canteenwala、Sammaiah Thota、Loon-Seng Tan、Kenneth Pritzker、Ying-Ying Huang、Sulbha K. Sharma、Divya Balachandran Kurup、Michael R. Hamblin、Brian Wilson、Augustine Urbas

  DOI：10.1039/c0jm00037j

  日期：——

  We report the synthesis of a new class of photoresponsive C60–DCE–diphenylaminofluorene nanostructures and their intramolecular photoinduced energy and electron transfer phenomena. Structural modification was made by chemical conversion of the keto group in C60(>DPAF-Cn) to a stronger electron-withdrawing 1,1-dicyanoethylenyl (DCE) unit leading to C60(>CPAF-Cn) with an increased electronic polarization of the molecule. The modification also led to a large bathochromic shift of the major band in visible spectrum giving measureable absorption up to 600 nm and extended the photoresponsive capability of C60–DCE–DPAF nanostructures to longer red wavelengths than C60(>DPAF-Cn). Accordingly, C60(>CPAF-Cn) may allow 2γ-PDT using a light wavelength of 1000–1200 nm for enhanced tissue penetration depth. Production efficiency of singlet oxygen by closely related C60(>DPAF-C2M) was found to be comparable with that of tetraphenylporphyrin photosensitizer. Remarkably, the 1O2 quantum yield of C60(>CPAF-C2M) was found to be nearly 6-fold higher than that of C60(>DPAF-C2M), demonstrating the large light-harvesting enhancement of the CPAF-C2M moiety and leading to more efficient triplet state generation of the C60> cage moiety. This led to highly effective killing of HeLa cells by C60(>CPAF-C2M) via photodynamic therapy (200 J cm−2 white light). We interpret the phenomena in terms of the contributions by the extended π-conjugation and stronger electron-withdrawing capability associated with the 1,1-dicyanoethylenyl group compared to that of the keto group.

  我们报告了一类新型光致伸缩性 C60âDCEâ 二苯胺芴纳米结构的合成及其分子内光诱导的能量和电子转移现象。通过化学方法将 C60(>DPAF-Cn) 中的酮基转化为电子吸附性更强的 1,1-二氰基乙烯（DCE）单元，对其进行了结构改造，从而得到了电子极化程度更高的 C60(>CPAF-Cn)。这种改性还导致可见光谱中的主要波段发生了很大的浴色偏移，使吸收波长达到 600 纳米，并将 C60âDCEâDPAF 纳米结构的光致发光能力扩展到比 C60(>DPAF-Cn) 更长的红色波长。因此，C60(>DPAF-Cn) 可以使用 1000â1200 nm 的光波长进行 2γ-PDT 以增强组织穿透深度。研究发现，密切相关的 C60(>DPAF-C2M) 产生单线态氧的效率与四苯基卟啉光敏剂相当。值得注意的是，C60(>CPAF-C2M) 的单线态氧量子产率比 C60(>DPAF-C2M) 高出近 6 倍，这表明 CPAF-C2M 分子的光收集能力大大增强，并导致 C60> 笼分子产生更高效的三重态。这导致 C60(>CPAF-C2M) 通过光动力疗法（200 J cmâ2 白光）高效杀死 HeLa 细胞。我们认为，与酮基相比，1,1-二氰基乙烯基具有扩展的Ï-共轭作用和更强的电子吸收能力。