3,5-dimethyl-4-(10-bromoanthracenyl)julolidine | 1008788-37-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 3,5-dimethyl-4-(10-bromoanthracenyl)julolidine
• 英文别名: 3,5-dimethyl-4-(10-bromoanthracen-9-yl)julolidine
• CAS: 1008788-37-1
• 化学式: C₂₈H₂₆BrN
• 分子量: 456.425
• InChiKey: LVHZJXZQWKWOET-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.74
• 重原子数：
  30.0
• 可旋转键数：
  1.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  3.24
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  芴-9-羰基-2-硼酸频哪酯 、 3,5-dimethyl-4-(10-bromoanthracenyl)julolidine 在 四(三苯基膦)钯 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以67%的产率得到
  参考文献：
  名称：

  Exponential Distance Dependence of Photoinitiated Stepwise Electron Transfer in Donor–Bridge–Acceptor Molecules: Implications for Wirelike Behavior

  摘要：

  Donor-bridge-acceptor (D-B-A) systems in which a 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An) chromophore and a naphthalene-1,8:4,5-bis(dicarboximide) (NI) acceptor are linked by oligomeric 2,7-fluorenone (FNn) bridges (n = 1-3) have been synthesized. Selective photoexcitation of DMJ-An quantitatively produces DMJ(+center dot)-An(-center dot), and An(-center dot)acts as a high-potential electron donor. Femtosecond transient absorption spectroscopy in the visible and mid-IR regions showed that electron transfer occurs quantitatively in the sequence: DMJ(+center dot)-An(-center dot)-FNn-NI -> DMJ(+center dot)-An-FNn-center dot-NI -> DMJ(+center dot)-An-FNn-NI-center dot. The charge-shift reaction from An(-center dot) to NI-center dot exhibits an exponential distance dependence in the nonpolar solvent toluene with an attenuation factor (beta) of 0.34 angstrom(-1), which would normally be attributed to electron tunneling by the superexchange mechanism. However, the FNn-center dot radical anion was directly observed spectroscopically as an intermediate in the charge-separation mechanism, thereby demonstrating conclusively that the overall charge separation involves the incoherent hopping (stepwise) mechanism. Kinetic modeling of the data showed that the observed exponential distance dependence is largely due to electron injection onto the first FN unit followed by charge hopping between the FN units of the bridge biased by the distance-dependent electrostatic attraction of the two charges in D+center dot-B-center dot-A. This work shows that wirelike behavior does not necessarily result from building a stepwise, energetically downhill redox gradient into a D-B-A molecule.

  DOI：

  10.1021/ja205913q

文献信息

• Controlling Electron Transfer in Donor−Bridge−Acceptor Molecules Using Cross-Conjugated Bridges
  作者：Annie Butler Ricks、Gemma C. Solomon、Michael T. Colvin、Amy M. Scott、Kun Chen、Mark A. Ratner、Michael R. Wasielewski

  DOI：10.1021/ja107420a

  日期：2010.11.3

  xanthone bridges. Photoinitiated CS through the cross-conjugated 1,1-diphenylethene bridge is about 30 times slower than through its linearly conjugated trans-stilbene counterpart and is comparable to that observed through the diphenylmethane bridge. This result implies that cross-conjugation strongly decreases the π orbital contribution to the donor-acceptor electronic coupling so that electron transfer

  已经使用时间分辨光谱比较和对比了一系列具有交叉共轭、线性共轭和饱和桥的供体-桥-受体 (DBA) 分子中的光引发电荷分离 (CS) 和重组 (CR)。3,5-二甲基-4-(9-蒽基)julolidine (DMJ-An) 的光激发电荷转移态是供体，萘-1,8:4,5-双(二甲酰亚胺) (NI) 是受体在所有情况下，连同 1,1-二苯基乙烯、反式二苯乙烯、二苯基甲烷和氧杂蒽酮桥。通过交叉共轭 1,1-二苯基乙烯桥的光引发 CS 比通过其线性共轭反式二苯乙烯对应物慢约 30 倍，并且与通过二苯甲烷桥观察到的结果相当。该结果意味着交叉共轭强烈降低了对供体-受体电子耦合的 π 轨道贡献，因此电子转移很可能使用桥 σ 系统作为其主要的 CS 途径。相比之下，通过交叉共轭的呫吨酮桥的 CS 速率与通过线性共轭的反二苯乙烯桥观察到的速率相当。这些桥上的分子电导计算表明，交叉共轭导致量子干涉效应，极大地改
• Carmieli, Raanan; Mi, Qixi; Ricks, Annie Butler, Journal of the American Chemical Society, 2009, vol. 131, p. 8372 - 8373
  作者：Carmieli, Raanan、Mi, Qixi、Ricks, Annie Butler、Giacobbe, Emilie M.、Mickley, Sarah M.、Wasielewski, Michael R.

  DOI：——

  日期：——
• Spin-Selective Charge Transport Pathways through <i>p-</i>Oligophenylene-Linked Donor−Bridge−Acceptor Molecules
  作者：Amy M. Scott、Tomoaki Miura、Annie Butler Ricks、Zachary E. X. Dance、Emilie M. Giacobbe、Michael T. Colvin、Michael R. Wasielewski

  DOI：10.1021/ja907625k

  日期：2009.12.9

  A series of donor-bridge-acceptor (D-B-A) triads have been synthesized in which the donor, 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An), and the acceptor, naphthalene-1,8:4,5-bis(dicarboximide) (NI), are linked by p-oligophenylene (Ph-n) bridging units (n = 1-5). Photoexcitation of DMJ-An produces DMJ(+center dot)-An(-center dot) quantitatively, so that An(-center dot) acts as a high potential electron donor, which rapidly transfers an electron to NI yielding a long-lived spin-coherent radical ion pair (DMJ(+center dot)-An-Ph-n-NI-center dot). The charge transfer properties of 1-5 have been studied using transient absorption spectroscopy, magnetic field effects (MFEs) on radical pair and triplet yields, and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The charge separation (CS) and recombination (CR) reactions exhibit exponential distance dependencies with damping coefficients of beta = 0.35 angstrom(-1) and 0.34 angstrom(-1), respectively. Based on these data, a change in mechanism from superexchange to hopping was not observed for either process in this system. However, the CR reaction is spin-selective and produces the singlet ground state and both (3)*An and (3)*NI. A kinetic analysis of the MFE data shows that superexchange dominates both pathways with beta = 0.48 angstrom(-1) for the singlet CR pathway and beta = 0.35 angstrom(-1) for the triplet CR pathway. MFEs and TREPR experiments were used to measure the spin-spin exchange interaction, 2J, which is directly related to the electronic coupling matrix element for CR, V-CR(2). The magnitude of 2J also shows an exponential distance dependence with a damping coefficient alpha = 0.36 angstrom(-1), which agrees with the P values obtained from the distance dependence for triplet CR. These results were analyzed in terms of the bridge molecular orbitals that participate in the charge transport mechanism.