7-α-bromoacetyl-9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene | 887951-51-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 7-α-bromoacetyl-9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene
• 英文别名: 2-bromo-1-[7-(N-phenylanilino)-9,9-bis(3,5,5-trimethylhexyl)fluoren-2-yl]ethanone
• CAS: 887951-51-1
• 化学式: C₄₅H₅₆BrNO
• 分子量: 706.85
• InChiKey: WIBYBTNWLOBHLX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.4
• 重原子数：
  48
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.44
• 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-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70%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：

  Synthesis and characterization of photoresponsive diphenylaminofluorene chromophore adducts of [60]fullerene

  摘要：

  合成了一类接受体-酮-供体结构，包括受阻的9,9-二（3,5,5-三甲基己基）-2-二苯胺氟烯-美琅[60]富勒烯C60(>DPAF-C9)及相关的双加合物C60(>DPAF-C9)2和C60(>DPAF-C2)2。它们是多光子吸收C60(>DPAF-C2)的衍生物，在激光激发下800 nm的纳秒区域显示出增强的同时两光子吸收截面。这些C60-DPAF共轭物的分子合成涉及通过酮联结将二苯氨基氟烯部分共价连接到美琅[60]富勒烯上，以增加分子的接受体-供体极性，与富勒烯笼体结合。7-(1,2-二氢-1,2-美琅富勒烯[60]-61-羰基)-9,9-二烷基-2-二苯胺氟烯C60(>DPAF-Cn)的制备涉及用关键合成单元7-α-溴乙酰-9,9-二烷基-2-二苯胺氟烯对C60进行环丙烷化。该合成单元的合成通过三步法实现，起始于2-溴氟烯，通过对氟烯环的C9位的双烷基化，在双烷基氟烯的C2位上连接二苯胺基团，以及在二苯胺氟烯的C7位对α-溴乙酰基进行弗riedel-Craft酰化。所有C60-DPAF衍生物均经过全面表征，化学结构通过各种光谱分析确认，并通过C60(>DPAF-C2)的单晶结构分析数据进行验证。观察到C60(>DPAF-C2)、C60(>DPAF-C9)和C60(>DPAF-C9)2的强溶剂敏感荧光猝灭现象，在更极性溶剂（如DMF、PhCN和THF）中未观察到700 nm以上的荧光带，而在较少极性的溶剂（如甲苯、CHCl3和CS2）中观察到700-710 nm的富勒烯荧光带。这归因于在前一组溶剂中，通过富勒烯部分的单态激发态1C60*(>DPAF-Cn)发生电子转移。相反，在后者溶剂组中，DPAF-Cn部分向富勒烯笼体的能量转移过程更加有利。

  DOI：

  10.1039/b515055h
• 作为产物：
  描述：

  2-溴芴 在 aluminum (III) chloride 、 potassium tert-butylate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 16.0h， 生成 7-α-bromoacetyl-9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluorene
  参考文献：
  名称：

  Synthesis of Photoswitchable Magnetic Au–Fullerosome Hybrid Nanomaterials for Permittivity Enhancement Applications

  摘要：

  我们设计并合成了几种三层核壳（γ-FeOx@AuNP）@[C60(>DPAF-C9)1或2]n纳米粒子（NPs）。这些外层具有可极化全极化结构的纳米粒子是由高磁性核壳γ-FeOx@AuNPs制成的。研究发现，3的全原子极化能够导致材料介电常数的大幅放大，这也与0.5-4.0 GHz频率范围内的光开关效应有关。多层合成结构允许金层中光诱导的累积表面等离子体共振（SPR）能量在直接接触的近场中向部分双层 C60(>DPAF-C9)1 或 2 衍生的全原子膜壳层进行佛斯特共振能量转移（FRET），而不会产生通常与 SPR 相关的辐射热。

  DOI：

  10.3390/molecules200814746

文献信息

• Synthesis and characterization of photoresponsive diphenylaminofluorene chromophore adducts of [60]fullerene
  作者：Prashant A. Padmawar、Taizoon Canteenwala、Sarika Verma、Loon-Seng Tan、Long Y. Chiang

  DOI：10.1039/b515055h

  日期：——

  A class of acceptor–keto–donor structures as hindered 9,9-di(3,5,5-trimethylhexyl)-2-diphenylaminofluoreno-methano[60]fullerene C60(>DPAF-C9) and the related bisadducts C60(>DPAF-C9)2 and C60(>DPAF-C2)2 were synthesized. They are derivatives of multiphoton absorptive C60(>DPAF-C2) showing enhanced cross-sections of simultaneous two-photon absorption under laser excitation at 800 nm in nanosecond region. Molecular synthesis of these C60–DPAF conjugates involved the covalent attachment of a diphenylaminofluorene moiety to methano[60]fullerene via a keto linkage for increasing molecular acceptor–donor polarization of the chromophore in conjunction with the fullerene cage. Preparation of 7-(1,2-dihydro-1,2-methanofullerene[60]-61-carbonyl)-9,9-dialkyl-2-diphenylaminofluorene C60(>DPAF-Cn) involved cyclopropanation of C60 with a key synthon 7-α-bromoacetyl-9,9-dialkyl-2-diphenylaminofluorene. Synthesis of this synthon was achieved by a three-steps procedure starting from 2-bromofluorene via dialkylation at C9 of the fluorene ring, attachment of a diphenylamino group at C2 of dialkylfluorene, and Friedel–Craft acylation of the α-bromoacetyl group at C7 of diphenylaminofluorene. All C60–DPAF derivatives were fully characterized with the chemical structures confirmed by various spectroscopic analyses and validated by the single-crystal structural analysis data of C60(>DPAF-C2). Strong solvent-sensitive fluorescence quenching phenomena of C60(>DPAF-C2), C60(>DPAF-C9), and C60(>DPAF-C9)2 were noticed, showing no fluorescence band above 700 nm in more polar solvents, such as DMF, PhCN, and THF, while in less polar solvents (toluene, CHCl3, and CS2) a fullerenyl fluorescence band at 700–710 nm was observed. It was attributed to the occurrence of electron transfer via the singlet excited state of the fullerene moiety 1C60*(>DPAF-Cn) in the former group of the solvents. On the contrary, energy transfer processes from DPAF-Cn moiety to the fullerene cage are favored in the latter group of the solvents.

  合成了一类接受体-酮-供体结构，包括受阻的9,9-二（3,5,5-三甲基己基）-2-二苯胺氟烯-美琅[60]富勒烯C60(>DPAF-C9)及相关的双加合物C60(>DPAF-C9)2和C60(>DPAF-C2)2。它们是多光子吸收C60(>DPAF-C2)的衍生物，在激光激发下800 nm的纳秒区域显示出增强的同时两光子吸收截面。这些C60-DPAF共轭物的分子合成涉及通过酮联结将二苯氨基氟烯部分共价连接到美琅[60]富勒烯上，以增加分子的接受体-供体极性，与富勒烯笼体结合。7-(1,2-二氢-1,2-美琅富勒烯[60]-61-羰基)-9,9-二烷基-2-二苯胺氟烯C60(>DPAF-Cn)的制备涉及用关键合成单元7-α-溴乙酰-9,9-二烷基-2-二苯胺氟烯对C60进行环丙烷化。该合成单元的合成通过三步法实现，起始于2-溴氟烯，通过对氟烯环的C9位的双烷基化，在双烷基氟烯的C2位上连接二苯胺基团，以及在二苯胺氟烯的C7位对α-溴乙酰基进行弗riedel-Craft酰化。所有C60-DPAF衍生物均经过全面表征，化学结构通过各种光谱分析确认，并通过C60(>DPAF-C2)的单晶结构分析数据进行验证。观察到C60(>DPAF-C2)、C60(>DPAF-C9)和C60(>DPAF-C9)2的强溶剂敏感荧光猝灭现象，在更极性溶剂（如DMF、PhCN和THF）中未观察到700 nm以上的荧光带，而在较少极性的溶剂（如甲苯、CHCl3和CS2）中观察到700-710 nm的富勒烯荧光带。这归因于在前一组溶剂中，通过富勒烯部分的单态激发态1C60*(>DPAF-Cn)发生电子转移。相反，在后者溶剂组中，DPAF-Cn部分向富勒烯笼体的能量转移过程更加有利。
• 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。
• 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 of Photoswitchable Magnetic Au–Fullerosome Hybrid Nanomaterials for Permittivity Enhancement Applications
  作者：Min Wang、Seaho Jeon、Chefu Su、Tzuyang Yu、Loon-Seng Tan、Long Chiang

  DOI：10.3390/molecules200814746

  日期：——

  We designed and synthesized several nanomaterials 3 of three-layered core-shell (γ-FeOx@AuNP)@[C60(>DPAF-C9)1or2]n nanoparticles (NPs). These NPs having e−-polarizable fullerosome structures located at the outer layer were fabricated from highly magnetic core-shell γ-FeOx@AuNPs. Fullerosomic polarization of 3 was found to be capable of causing a large amplification of material permittivity that is also associated with the photoswitching effect in the frequency range of 0.5‒4.0 GHz. Multilayered synthetic construction allows Förster resonance energy transfer (FRET) of photoinduced accumulative surface plasmon resonance (SPR) energy in the gold layer to the partially bilayered C60(>DPAF-C9)1or2-derived fullerosome membrane shell layer in a near-field of direct contact without producing radiation heat, which is commonly associated with SPR.

  我们设计并合成了几种三层核壳（γ-FeOx@AuNP）@[C60(>DPAF-C9)1或2]n纳米粒子（NPs）。这些外层具有可极化全极化结构的纳米粒子是由高磁性核壳γ-FeOx@AuNPs制成的。研究发现，3的全原子极化能够导致材料介电常数的大幅放大，这也与0.5-4.0 GHz频率范围内的光开关效应有关。多层合成结构允许金层中光诱导的累积表面等离子体共振（SPR）能量在直接接触的近场中向部分双层 C60(>DPAF-C9)1 或 2 衍生的全原子膜壳层进行佛斯特共振能量转移（FRET），而不会产生通常与 SPR 相关的辐射热。