31,32:55,56-bis[bis(ethoxycarbonyl)methano]-31,32,55,56-tetrahydro[60]fullerene | 155382-68-6

• 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: 31,32:55,56-bis[bis(ethoxycarbonyl)methano]-31,32,55,56-tetrahydro[60]fullerene
• 英文别名: e-C62(COOEt)4；tetraethyl 1,2:18,36-bis(methano)[60]fullerene-61,61,62,62-tetracarboxylate
• CAS: 155382-68-6
• 化学式: C₇₄H₂₀O₈
• 分子量: 1036.97
• InChiKey: BUHXQPORYBFJJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.6
• 重原子数：
  82
• 可旋转键数：
  12
• 环数：
  34.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  溴代丙二酸二乙酯 、 31,32:55,56-bis[bis(ethoxycarbonyl)methano]-31,32,55,56-tetrahydro[60]fullerene 以40%的产率得到eee-C63(COOEt)6
  参考文献：
  名称：

  Redox and Excitation Studies with C60-Substituted Malonic Acid Diethyl Esters

  摘要：

  Flash photolytic formation of excited triplet states, their consecutive reductive quenching with diazabicyclooctane (DABCO), and pulse radiolytic formation of pi-radical anions of various Cao-derivatives have been recorded. The fullerenes were functionalized via single, double, and triple cyclopropylation of C-60 with bromomalonic acid diethyl ester. Flash photolytic irradiation at 308 nm of these C-60 derivatives in toluene solution yielded triplet excited states which exhibited a strong blue shift of lambda(max) by nearly 100 nm as compared to plain C-3(60). This is rationalized in terms of a gradual destruction of the fullerene's pi-system with an increasing number of bis(ethoxycarbonyl)methylene groups. The blue shift coincides with a significant slow down for the rate of reductive quenching of the excited triplet states by DABCO, i.e., 1.3 x 10(6) M(-1) s(-1) vs 2.5 x 10(9) M(-1) s(-1) for the quenching of equatorial-(C-3(60))[C(COOEt)(2)](3) and C-3(60), respectively. The radical-induced reduction of functionalized C-60 has been studied in a toluene/acetone/2-propanol mixture by means of time-resolved pulse radiolysis with measurements being conducted in the characteristic near-IR region. An almost linear dependence is obtained between the energy of the most significant IR-pi-radical anion band versus the number of bis(ethoxycarbonyl)methylene groups at the fullerene core, with the respective lambda(max) ranging from 1080 nm for C-60(.-) to 1015 nm for equatorial-(C-60(.-))[C(COOEt)(2)](3). A corresponding trend emerges from cyclic voltammetry measurements on the redox potential in toluene/2-propanol. They show a difference of 330 mV between the formation of C-60(.-) (E(1/2) = -0.55 V vs SCE) and the first reduction of equatorial-C-60-[C(COOEt)(2)](3) (E(1/2) = -0.86 V vs SCE). It appears that all these physicochemical parameters very sensitively reflect the site and degree of functionalization of C-60.

  DOI：

  10.1021/j100023a013
• 作为产物：
  描述：

  以 甲苯 为溶剂， 以98 %的产率得到31,32:55,56-bis[bis(ethoxycarbonyl)methano]-31,32,55,56-tetrahydro[60]fullerene
  参考文献：
  名称：

  通过精确合成具有调节分子堆积的单一异构体富勒烯双加合物实现高效锡基钙钛矿太阳能电池

  摘要：

  设计和合成具有较高导带最小值的富勒烯双加合物有望进一步提高锡基钙钛矿太阳能电池（TPSC）的器件性能。然而，通常获得的富勒烯双加合物产物是异构体混合物，需要复杂的分离。此外，异构体混合物容易导致能量排列紊乱、界面电荷损失和有限的器件性能改进。在此，我们利用空间位阻辅助策略合成了单一异构体C 60和C 70基丙二酸二乙酯官能化双加合物（C 60 BB 和C 70 BB），并确定了单晶衍射涉及的所有分子结构。同时，我们发现用于加工富勒烯双加合物的不同溶剂可以有效调节其薄膜中的分子堆积。使用苯甲醚制备的致密且无定形的富勒烯双加合物薄膜表现出最高的电子迁移率。最后，基于 C 60 BB 和 C 70 BB 的 TPSC 表现出令人印象深刻的效率，分别高达 14.51% 和 14.28%。这些器件还表现出出色的长期稳定性。这项工作强调了开发合成单异构体富勒烯双加合物并调节其分子堆积以提高 TPSC 性能的策略的重要性。

  DOI：

  10.1021/jacs.3c10515

文献信息

• Macrocyclization on the fullerene core: Direct regio- and diastereoselective multi-functionalization of [60]fullerene, and synthesis of fullerene-dendrimer derivatives
  作者：Jean-François Nierengarten、Tilo Habicher、Roland Kessinger、Francesca Cardullo、François Diederich、Volker Gramlich、Jean-Paul Gisselbrecht、Corinne Boudon、Maurice Gross

  DOI：10.1002/hlca.19970800721

  日期：1997.11.3

  induce dramatic changes in the chiroptical properties of the tether chromophore such as strong enhancement and reversal of sign of the Cotton effects in the circular dichroism (CD) spectra (Figs. 4 and 5). By the same method, the functionafized bis-adducts 50 and 51 (Schemes 10 and 11) were prepared as initiator cores for the synthesis of the fullerene dendrimers 62, 63, and 66 (Schemes 12 and 13) by

  双重Bingel反应中的buckminsterfullerene，C 60和双丙二酸酯衍生物之间的大环化为制备具有高区域选择性和非对映选择性的C 60的共价双加合物提供了一种通用而简单的方法。光谱分析，立体化学因素和X射线晶体学的结合（图2）表明，在可能的进，出和出立体异构体中，双丙二酸酯的反应由o-联结，间-或对-亚二甲苯基系链仅提供外链式（方案1）。相反，使用衍生自1,10-菲咯啉的较大束缚物也提供了进出产品的第一个示例（±）-19（方案2）。从光学纯的双丙二酸酯衍生物开始，新的双官能化方法允许光学活性的富勒烯衍生物的非对映选择性制备（方案4和5），并最终实现了光学活性的顺式对映体的对映选择性制备（对映体过量ee> 97％）。3个双加合物，它们的手性完全由加成模式引起（图6）。具有光学活性的9,9'-spirobi [9 H]的双丙二酸酯的大环固定-芴]衍生的系绳至C 60下产生的24和耳鼻喉科-
• Regioselectivity of Multiple Cyclopropanations of C60 and Introduction of a General Bond-Labeling Algorithm for Fullerenes and Their Derivatives
  作者：Andreas Hirsch、Irs Lamparth、Georg Schick

  DOI：10.1002/jlac.199619961105

  日期：1996.11

  which shows that the observed regioselectivities of multiple cyclopropanations of C60 are due to orbital-allowed processes. Next to the coefficients of frontier orbitals the characteristic cage distortions of the oligomethanofullerenes are discussed. For further experimental corroboration the synthesis and characterization of an unsymmetrical trisadduct with a I, eI, III*-addition pattern are described

  进行了计算（AM1）分析，该分析表明，观察到的C 60的多个环丙烷的区域选择性是由于轨道允许的过程所致。除边界轨道系数外，还讨论了低聚甲基富勒烯的特征笼形畸变。为了进一步的实验证实，描述了具有I，eI，III *加成模式的不对称三加合物的合成和表征。此外，由于对C 60的导数中的加成模式进行了系统的描述性分配 随着更高的富勒烯变得越来越重要，引入了一种简单而通用的算法，该算法可以对[6,6]-和[5,6]-键进行明确的键标记以及对任何富勒烯的绝对构型进行分配衍生物。
• Photophysical and Electron-Transfer Properties of Mono- and Multiple-Functionalized Fullerene Derivatives
  作者：Ya-Ping Sun、Radhakishan Guduru、Glenn E. Lawson、Jason E. Mullins、Zhixin Guo、Jessica Quinlan、Christopher E. Bunker、James R. Gord

  DOI：10.1021/jp0000329

  日期：2000.5.1

  mono-functionalized C60 derivatives, the compound with a [5,6]-open fulleroid addition pattern on the fullerene cage appeared to be considerably less fluorescent than those with a [6,6]-closed cage addition pattern. Despite the disturbance of the electronic structure via multiple additions to the fullerene cage, the multiple-functionalized C60 derivatives exhibited no dramatic changes in fluorescence quantum

  合成了单官能化和多官能化 C60 衍生物并研究了它们的光物理性质。测量并比较了溶液中 C60 衍生物的电子吸收光谱和吸收率。通过使用近红外敏感发射光谱仪记录荧光光谱，我们定量确定了 C60 衍生物的荧光量子产率。对于单官能化的 C60 衍生物，在富勒烯笼上具有 [5,6]-开富勒体加成模式的化合物的荧光似乎比具有 [6,6]-闭笼加成模式的化合物低得多。尽管通过多次添加富勒烯笼扰乱了电子结构，与单官能化 C60 衍生物相比，多官能化 C60 衍生物的荧光量子产率没有显着变化。使用时间相关单光子计数技术获得的 C60 衍生物的荧光寿命均在 ...
• Efficient Tin-Based Perovskite Solar Cells Enabled by Precisely Synthesized Single-Isomer Fullerene Bisadducts with Regulated Molecular Packing
  作者：Panpan Yang、Chao Sun、Xifeng Fu、Shuo Cheng、Jingfu Chen、Hui Zhang、Zi-Ang Nan、Jinxin Yang、Xin-Jing Zhao、Li-Qiang Xie、Lingyi Meng、Chengbo Tian、Zhanhua Wei

  DOI：10.1021/jacs.3c10515

  日期：2024.1.31

  Designing and synthesizing fullerene bisadducts with a higher-lying conduction band minimum is promising to further improve the device performance of tin-based perovskite solar cells (TPSCs). However, the commonly obtained fullerene bisadduct products are isomeric mixtures and require complicated separation. Moreover, the isomeric mixtures are prone to resulting in energy alignment disorders, interfacial

  设计和合成具有较高导带最小值的富勒烯双加合物有望进一步提高锡基钙钛矿太阳能电池（TPSC）的器件性能。然而，通常获得的富勒烯双加合物产物是异构体混合物，需要复杂的分离。此外，异构体混合物容易导致能量排列紊乱、界面电荷损失和有限的器件性能改进。在此，我们利用空间位阻辅助策略合成了单一异构体C 60和C 70基丙二酸二乙酯官能化双加合物（C 60 BB 和C 70 BB），并确定了单晶衍射涉及的所有分子结构。同时，我们发现用于加工富勒烯双加合物的不同溶剂可以有效调节其薄膜中的分子堆积。使用苯甲醚制备的致密且无定形的富勒烯双加合物薄膜表现出最高的电子迁移率。最后，基于 C 60 BB 和 C 70 BB 的 TPSC 表现出令人印象深刻的效率，分别高达 14.51% 和 14.28%。这些器件还表现出出色的长期稳定性。这项工作强调了开发合成单异构体富勒烯双加合物并调节其分子堆积以提高 TPSC 性能的策略的重要性。
• 2,6-Dimethoxyanthracene — a directing group for regioselective bisaddition to C60
  作者：Stephen R. Wilson、Qing Lu

  DOI：10.1016/0040-4039(95)01111-t

  日期：1995.8