di-tert-butyl methano[60]fullerene-61,61-dicarboxylate

• 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: di-tert-butyl methano[60]fullerene-61,61-dicarboxylate
• 化学式: C₇₁H₁₈O₄
• 分子量: 934.922
• InChiKey: UOWWDPWRBVBHKR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16
• 重原子数：
  75
• 可旋转键数：
  6
• 环数：
  33.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  di-tert-butyl methano[60]fullerene-61,61-dicarboxylate 以 邻二氯苯 为溶剂， 反应 6.0h， 以100%的产率得到叔丁基(1,2-亚甲基富勒烯C60)-61-羧酸酯
  参考文献：
  名称：

  Methanofullerenes, C₆₀(CH₂)_n (n = 1, 2, 3), as Building Blocks for High-Performance Acceptors Used in Organic Solar Cells

  摘要：

  Selective preparation of C-60(CH2)n (n = 1, 2, 3) was realized via a "Bingel-decarboxylation" route. A 54 pi-electron derivative of C-60(CH2)(2), OQBMF, demonstrates an outstanding power conversion efficiency (PCE) of 6.43% (V-oc = 0.95 V, J(sc),c = 9.67 mA cm(-2), FF = 70%) in fullerene:P3HT solar cells since the small CH2 addends lift up fullerene LUMO and increase V-oc, significantly without decreasing mobility significantly.

  DOI：

  10.1021/ol4035275
• 作为产物：
  描述：

  di-tert-butyl 2-bromomalonate 、 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 2.0h， 以63%的产率得到di-tert-butyl methano[60]fullerene-61,61-dicarboxylate
  参考文献：
  名称：

  Thermo-cleavable fullerene materials as buffer layers for efficient polymer solar cells

  摘要：

  一类新的可热裂解富勒烯，即二叔丁基甲桥[60]富勒烯-61,61-二甲酸酯（DBMD）、双（2-甲基己烷-2-基）甲桥[60]富勒烯-61,61-二甲酸酯（BMHMD）以及二叔丁基甲桥[60]富勒烯-61,61-二甲酸酯双加合物（bis-adducts）、61-二羧酸盐 (BMHMD) 和甲桥[60]富勒烯-61,61-二羧酸二叔丁酯加合物 (bis-DBMD)。在高温下，这三种化合物的叔烷基酯基发生热裂解过程，生成不溶性的甲桥[60]富勒烯-61-羧酸（MCAs）。BMHMD 和双-DBMD 被用作倒置聚合物太阳能电池的阴极缓冲层。加热氧化锌上的 BMHMD 或双-DBMD 薄膜可分别产生 MCA1 和 MCA2 界面层。MCA 改性氧化锌的表面更光滑、更疏水，并显示出优异的耐溶剂性。MCA 缓冲层通过提高太阳能电池的 Jsc 和 FF 显著改善了器件性能。P3HT/PC61BM 太阳能电池的功率转换效率（PCE）从 3.44%（对照）提高到 3.79%（MCA1）和 4.10%（MCA2），PBDTTT-C/PC71BM 太阳能电池的功率转换效率（PCE）从 6.95%（对照）提高到 7.13%（MCA1）和 7.57%（MCA2）。

  DOI：

  10.1039/c3ta11811h

文献信息

• Anion−π Catalysis on Fullerenes
  作者：Javier López-Andarias、Antonio Frontera、Stefan Matile

  DOI：10.1021/jacs.7b08113

  日期：2017.9.27

  charge-delocalized enolate tautomers by anion-π interactions. Enolate-π interactions on fullerenes are much shorter than standard π-π interactions and anion-π interactions on planar surfaces, and alternative cation-π interactions are not observed. These findings open new perspectives with regard to anion-π interactions in general and the use of carbon allotropes in catalysis.

  富勒烯上的阴离子-π 相互作用与富勒烯在催化中的应用一样缺乏探索。然而，强大的交换相关贡献和它们表面上的局部 π 孔保证了独特的选择性。为了详细说明这一承诺，附近附有叔胺。取决于它们的位置，由此产生的富勒烯阴离子过渡态的稳定性显示出加速不利的烯醇加成和对映选择性的外狄尔斯-阿尔德反应。发现的选择性与计算模拟一致，特别是关于通过阴离子-π 相互作用区分不同平面化和电荷离域的烯醇互变异构体。富勒烯上的烯醇-π相互作用比平面上的标准π-π相互作用和阴离子-π相互作用短得多，并没有观察到替代的阳离子-π 相互作用。这些发现为阴离子-π相互作用以及碳同素异形体在催化中的应用开辟了新的视角。
• Thermo-cleavable fullerene materials as buffer layers for efficient polymer solar cells
  作者：Shan Chen、Xiaoyan Du、Gang Ye、Jiamin Cao、Hao Sun、Zuo Xiao、Liming Ding

  DOI：10.1039/c3ta11811h

  日期：——

  A new class of thermo-cleavable fullerenes, di-tert-butyl methano[60]fullerene-61,61-dicarboxylate (DBMD), bis(2-methylhexan-2-yl) methano[60]fullerene-61,61-dicarboxylate (BMHMD), and di-tert-butyl methano[60]fullerene-61,61-dicarboxylate bis-adducts (bis-DBMD), was facilely prepared through one-step Bingel reaction from C60. At high temperature, the tertiary alkyl ester groups of the three compounds undergo thermo-cleavage processes to produce insoluble methano[60]fullerene-61-carboxylic acids (MCAs). BMHMD and bis-DBMD were applied in inverted polymer solar cells as a cathode buffer layer. Heating BMHMD or bis-DBMD films on ZnO produced MCA1 and MCA2 interfacial layers, respectively. MCA-modified ZnO possesses a smoother and more hydrophobic surface, and shows excellent solvent-resistance. The MCA buffer layer dramatically improved the device performance by enhancing Jsc and FF of the solar cells. The power conversion efficiency (PCE) increased from 3.44% (control) to 3.79% (MCA1) and 4.10% (MCA2) for a P3HT/PC61BM solar cell, and from 6.95% (control) to 7.13% (MCA1) and 7.57% (MCA2) for a PBDTTT-C/PC71BM solar cell.

  一类新的可热裂解富勒烯，即二叔丁基甲桥[60]富勒烯-61,61-二甲酸酯（DBMD）、双（2-甲基己烷-2-基）甲桥[60]富勒烯-61,61-二甲酸酯（BMHMD）以及二叔丁基甲桥[60]富勒烯-61,61-二甲酸酯双加合物（bis-adducts）、61-二羧酸盐 (BMHMD) 和甲桥[60]富勒烯-61,61-二羧酸二叔丁酯加合物 (bis-DBMD)。在高温下，这三种化合物的叔烷基酯基发生热裂解过程，生成不溶性的甲桥[60]富勒烯-61-羧酸（MCAs）。BMHMD 和双-DBMD 被用作倒置聚合物太阳能电池的阴极缓冲层。加热氧化锌上的 BMHMD 或双-DBMD 薄膜可分别产生 MCA1 和 MCA2 界面层。MCA 改性氧化锌的表面更光滑、更疏水，并显示出优异的耐溶剂性。MCA 缓冲层通过提高太阳能电池的 Jsc 和 FF 显著改善了器件性能。P3HT/PC61BM 太阳能电池的功率转换效率（PCE）从 3.44%（对照）提高到 3.79%（MCA1）和 4.10%（MCA2），PBDTTT-C/PC71BM 太阳能电池的功率转换效率（PCE）从 6.95%（对照）提高到 7.13%（MCA1）和 7.57%（MCA2）。
• Electrochemistry of Mono- through Hexakis-adducts of C60
  作者：Corinne Boudon、Jean-Paul Gisselbrecht、Maurice Gross、Lyle Isaacs、Harry L. Anderson、R�diger Faust、Fran�ois Diederich

  DOI：10.1002/hlca.19950780523

  日期：1995.8.9

  methanofullerenes which prevent through-bond communication of substituent effects from the methano bridge to the fullerene sphere. In the series of mono- through hexakis-adducts 5–11, formed by tether-directed remote functionalization, reductions become increasingly difficult and more irreversible with increasing number of addends (see Table and Fig. 2). Whereas, in 0.1M Bu4NPF6/CH2Cl2, the first reduction of mono-adduct

  通过循环伏安法（CV）和在共价富勒烯衍生物（氧化还原性质的变化旋转圆盘电极（RDE）的第一系统的电化学研究2 - 11被报告为增加加数数目的函数）。Dialkynylmethanofullerenes 2 - 4经历多次，富勒烯为中心的还原步骤在比C稍微更负的电位60（1 ;参见表和图1）。哑铃形二聚体富勒烯衍生物4中的两个C球显示出独立的，相同的氧化还原特性。这突出了sp 3的绝缘特性甲基富勒烯中的-C原子可防止取代基效应从甲烷桥到富勒烯球的键合传递。在串联通过六加合物的单- 5 - 11，通过系绳定向远程官能形成，削减变得越来越困难和更不可逆的增加加数（见的数量表和图2）。而在0.1M Bu 4 NPF 6 / CH 2 Cl 2中，单加合物5的第一次还原在-1.06 V上相对于二茂铁/铁fer对（Fc / Fc +），六价加合物11发生。仅在-1.87 V时不可逆地还原。因此，随着富
• Balancing Attraction and Repulsion: The Influence of London Dispersion in [10]Cycloparaphenylene‐Fullerene Complexes
  作者：Jannis Volkmann、Daniel Kohrs、Hermann A. Wegner

  DOI：10.1002/chem.202300268

  日期：——

  The supramolecular assembly between substituted [10]cycloparaphenylene (s[10]CPP) and fullerenes was studied to investigate the subtle interplay of steric repulsion, conformation and attractive London dispersion interactions. For this, [10]CPP and a tert-butyl ester-substituted analogue were employed as host molecules whose fluorescence is quenched upon addition of C60 as well as alkyl malonyl ester-substituted

  研究了取代的 [10] 环对亚苯基 (s[10]CPP) 和富勒烯之间的超分子组装，以研究空间排斥、构象和有吸引力的伦敦分散相互作用的微妙相互作用。为此，[10]CPP 和叔丁酯取代的类似物被用作主体分子，其荧光在添加 C 60以及烷基丙二酰酯取代的富勒烯时被淬灭。
• Synthesis and Photodynamic Effect of New Highly Photostable Decacationically Armed [60]- and [70]Fullerene Decaiodide Monoadducts To Target Pathogenic Bacteria and Cancer Cells
  作者：Min Wang、Liyi Huang、Sulbha K Sharma、Seaho Jeon、Sammaiah Thota、Felipe F. Sperandio、Suhasini Nayka、Julie Chang、Michael R. Hamblin、Long Y. Chiang

  DOI：10.1021/jm3000664

  日期：2012.5.10

  Novel water-soluble decacationically armed C-60 and C-70 decaiodide monoadducts, C-60- and C-70[>M(C3N6+C3)(2)], were synthesized, characterized, and applied as photosensitizers and potential nano-PDT agents against pathogenic bacteria and cancer cells. A high number of cationic charges per fullerene cage and H-bonding moieties were designed for rapid binding to the anionic residues displayed on the outer parts of bacterial cell walls. In the presence of a high number of electron-donating iodide anions as parts of quaternary ammonium salts in the arm region, we found that C-70[>M(C3N6+C3)(2)] produced more HO center dot than C-60[>M(C3N6+C3)(2)], in addition to O-1(2). This finding offers an explanation of the preferential killing of Gram-positive and Gram-negative bacteria by C-60[>M(C3N6+C3)(2)] and C-70[>M(C3N6+C3)(2)], respectively. The hypothesis is that O-1(2) can diffuse more easily into porous cell walls of Gram-positive bacteria to reach sensitive sites, while the less permeable Gram-negative bacterial cell wall needs the more reactive HO center dot to cause real damage.