2-(Tetrathiafulvalenyl)pyrrolidino[3',4':1,2][60]fullerene | 159806-38-9

• 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: 2-(Tetrathiafulvalenyl)pyrrolidino[3',4':1,2][60]fullerene
• CAS: 159806-38-9
• 化学式: C₆₉H₉NS₄
• 分子量: 980.101
• InChiKey: AJEPSLUSIUXODQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.5
• 重原子数：
  74
• 可旋转键数：
  1
• 环数：
  35.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌 、 2-(Tetrathiafulvalenyl)pyrrolidino[3',4':1,2][60]fullerene 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Semiconducting charge transfer complexes from [60]Fullerene-tetrathiafulvalene (C60-TTF) systems

  摘要：

  The first CT-complexes of covalently bound [60]Fullerene-tetrathiafulvalene (TTF) systems with tetrafluorotetracyano-p-quinodimethane (TCNQF(4)) show a semiconducting behaviour. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0040-4039(96)01235-x
• 作为产物：
  描述：

  四硫富瓦烯 在 lithium diisopropyl amide 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 2-(Tetrathiafulvalenyl)pyrrolidino[3',4':1,2][60]fullerene
  参考文献：
  名称：

  Evidence for Two Separate One-Electron Transfer Events in Excited Fulleropyrrolidine Dyads Containing Tetrathiafulvalene (TTF)

  摘要：

  1,3-Dipolar cycloadditions of TTF-azomethine ylides (TTF = tetrathiafulvalene) to C-60 have been used to synthesize a series of novel donor-bridge-acceptor dyads. In these dyads the pyrrolidine[3',4':1,2][60]fullerene is covalently attached to the electron donor TTF either directly (5) or alternatively through one (2a) or two (7) vinyl groups. In the ground state, dyads 2a, 5, and 7 undergo Four quasireversible one-electron reductions and two reversible oxidation steps. The former are associated with the reduction of the C-60 core, whereas the latter correspond to the formation of the radical cation and dication of the TTF moiety, respectively. Semiempirical PM3 calculations reveal donor-acceptor distances of 4.8 Angstrom (5), 7.6 Angstrom (2a), and 10.5 Angstrom (7), and a deviation from planarity between the TTF fragment and the vinylogous spacer. In relation to an N-methylfulleropyrrolidine, the emission of the fullerene singlet excited state in dyads 2a, 5, and 7 is substantially reduced. Furthermore, the fluorescence quantum yield correlates well with the solvent dielectric constant and also with the spatial separation of the donor and acceptor moieties in the dyads. These correlation suggest that intramolecular electron-transfer processes evolving from the fullerene singlet excited state generate the (C-60(.-))-(TTF.+) pair. Pico- and nanosecond-resolved transient spectroscopy further substantiate a rapid transformation of the initially formed singlet excited state into the charge-separated radical pair with intramolecular rates ranging between 1.17 x 10(10) s(-1) and 1.47 x 10(9) s(-1). In all cases, the product of back electron transfer is the triplet excited state, which is generated with markedly high quantum yields (0.61-0.97). The latter is, in addition to the rapid primary intramolecular electron transfer, subject to a slower, secondary intermolecular electron transfer with rate constants of 7 x 10(8) M-1 s(-1) (5) in benzonitrile and 1.6 x 10(9) M-1 s(-1) (5) in toluene.

  DOI：

  10.1021/jp9941458

文献信息

• Evidence for Two Separate One-Electron Transfer Events in Excited Fulleropyrrolidine Dyads Containing Tetrathiafulvalene (TTF)
  作者：Nazario Martín、Luis Sánchez、M Angeles Herranz、Dirk M. Guldi

  DOI：10.1021/jp9941458

  日期：2000.5.1

  1,3-Dipolar cycloadditions of TTF-azomethine ylides (TTF = tetrathiafulvalene) to C-60 have been used to synthesize a series of novel donor-bridge-acceptor dyads. In these dyads the pyrrolidine[3',4':1,2][60]fullerene is covalently attached to the electron donor TTF either directly (5) or alternatively through one (2a) or two (7) vinyl groups. In the ground state, dyads 2a, 5, and 7 undergo Four quasireversible one-electron reductions and two reversible oxidation steps. The former are associated with the reduction of the C-60 core, whereas the latter correspond to the formation of the radical cation and dication of the TTF moiety, respectively. Semiempirical PM3 calculations reveal donor-acceptor distances of 4.8 Angstrom (5), 7.6 Angstrom (2a), and 10.5 Angstrom (7), and a deviation from planarity between the TTF fragment and the vinylogous spacer. In relation to an N-methylfulleropyrrolidine, the emission of the fullerene singlet excited state in dyads 2a, 5, and 7 is substantially reduced. Furthermore, the fluorescence quantum yield correlates well with the solvent dielectric constant and also with the spatial separation of the donor and acceptor moieties in the dyads. These correlation suggest that intramolecular electron-transfer processes evolving from the fullerene singlet excited state generate the (C-60(.-))-(TTF.+) pair. Pico- and nanosecond-resolved transient spectroscopy further substantiate a rapid transformation of the initially formed singlet excited state into the charge-separated radical pair with intramolecular rates ranging between 1.17 x 10(10) s(-1) and 1.47 x 10(9) s(-1). In all cases, the product of back electron transfer is the triplet excited state, which is generated with markedly high quantum yields (0.61-0.97). The latter is, in addition to the rapid primary intramolecular electron transfer, subject to a slower, secondary intermolecular electron transfer with rate constants of 7 x 10(8) M-1 s(-1) (5) in benzonitrile and 1.6 x 10(9) M-1 s(-1) (5) in toluene.
• Semiconducting charge transfer complexes from [60]Fullerene-tetrathiafulvalene (C60-TTF) systems
  作者：Nazario Martín、Luis Sánchez、Carlos Seoane、Raquel Andreu、Javier Garín、Jesús Orduna

  DOI：10.1016/0040-4039(96)01235-x

  日期：1996.8

  The first CT-complexes of covalently bound [60]Fullerene-tetrathiafulvalene (TTF) systems with tetrafluorotetracyano-p-quinodimethane (TCNQF(4)) show a semiconducting behaviour. Copyright (C) 1996 Elsevier Science Ltd