5,12-diethynyltetracene | 1198395-02-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 并四苯
• 英文名称: 5,12-diethynyltetracene
• 英文别名: 5,12-Diethynyltetracene
• CAS: 1198395-02-6
• 化学式: C₂₂H₁₂
• 分子量: 276.337
• InChiKey: BHRBHYWCQLBXAG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  trans diiodobis(triethylphosphine)platinum(II) 、 5,12-diethynyltetracene 在 copper(l) iodide HNEt₂ 作用下， 以 toluene 为溶剂， 以56%的产率得到[I(Et3P)2Pt]2-5,12-diethynyltetracene
  参考文献：
  名称：

  Gold(I) and Platinum(II) Tetracenes and Tetracenyldiacetylides: Structural and Fluorescence Color Changes Induced by σ-Metalation

  摘要：

  sigma-Metalation of tetracene can change the emission color of and introduce new structural dimensionality to the organic chromophore. Two synthetic entries to sigma-metallotetracenes have been explored, leading to emissive mononuclear (Ph3PAuI)-tetracene (1) and cis-[Br(Et3P)(2)Pt-II]-tetracene (2) and binuclear (R3PAu(I))(2)-tetracenyldiacetylide (R = Ph (4), Me (5)) and trans-[I(Et3P)(2)Pt-II](2)-tetracenyldiacetylide (6). Metalation can lower the emission energy of tetracene up to 0.53 eV. The X(Et3P)(2)Pt-II group (X = Br, I) has stronger perturbations on the tetracenyl ring than the R3PAu(I) group. sigma-Metalation also leads to different crystal packing of the complexes and thus arrangements of the tetracenyl rings. Aurophilic attraction operates in 5, leading to self-assembly of the molecules into a novel honeycomb structure composed of helical Au-I chains. In contrast to the other complexes, the crystal of 5 is not emissive, possibly due to efficient exciton delocalization.

  DOI：

  10.1021/om100046h
• 作为产物：
  描述：

  5,12-萘并萘醌 在 甲醇 、 正丁基锂 、 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 生成 5,12-diethynyltetracene
  参考文献：
  名称：

  具有不同能量转移效率的手性控制的超分子供体-受体共聚

  摘要：

  手性为超分子聚合物领域提供了巨大的价值，不仅可以作为监测动态组装过程的探针，还可以提供对手性材料的访问。目前的研究表明，对于超分子供体-受体共聚物，它们的共聚单体组织模式可以在分子水平上受到立体通信的极大影响。对映纯N -[(1 R或 1 S)-苯乙基]苯甲酰胺结合到两个结构相似的共聚单体中，位于 π-芳族二乙炔核心和烷基链外围之间。立体甲基单元的平行排列带来了同手性共聚单体之间的空间位阻，而异手性共聚单体由于采用交错排列而减轻了空间位阻。因此，它为纳米纤维内的纯手性超分子共聚物引导随机混合组织。相比之下，异手性对应物以交替的供体 - 受体组织方式形成纳米颗粒。共聚单体排列模式的变化导致了超分子水平上不同的能量转移效率。全面的，

  DOI：

  10.1021/jacs.2c02270

文献信息

• Oxidized divinyl oligoacene-bridged diruthenium complexes: bridged localized radical characters and reduced aromaticity in bridge cores
  作者：Ya-Ping Ou、Jing Zhang、Yuxuan Hu、Jun Yin、Chunyan Chi、Sheng Hua Liu

  DOI：10.1039/d0dt02883e

  日期：——

  predicted via time-dependent DFT calculations suggested that strong bridged ligands participate in redox processes. NIR absorptions were not observed in complexes 4+ and 5+ possibly because of instability in their twisted and noncoplanar geometry. Electron paramagnetic resonance results and spin density distribution demonstrated that the bridged localized degrees of 1+–5+ successively increased with the extension

  合成了一系列由低聚乙炔桥接的双金属钌乙烯基复合物1-5，并进行了表征。1-5的比较循环伏安法结果表明，随着共轭配体的延伸，第一氧化电位逐渐降低。在氧化时，以单独使用氧化物质1 + - 5 +，相当小的ν（CO）改变所预测的红外（IR）光谱和的金属到配体的电荷转移吸收在近IR中的特征带（NIR）区域通过时间依赖的DFT计算表明强桥联配体参与了氧化还原过程。在复合物中未观察到NIR吸收4 +和5 +可能是因为它们的扭曲和非共面几何形状不稳定。电子顺磁共振结果和自旋密度分布证明，随着寡并苯从苯到并四苯的延伸，桥连的1 + – 5 +的局域化程度依次增加。对中性分子和单阳离子对桥芯的芳香性和π电子密度的进一步比较分析表明，氧化后，芳香族自由基逐渐转变为喹啉自由基。
• Acene Size‐Dependent Transition of The Radical Centers From the Metal to The Acene Parts In Monocationic Dinuclear (Diethynylacene)diyl Complexes
  作者：Yuya Tanaka、Reo Kawano、Munetaka Akita

  DOI：10.1002/chem.202201358

  日期：2022.10.4

  Charge-delocalization of various monocationic diruthenium (p-diethynylacene)diyl complexes was investigated. The distribution of the radical centers is dependent on the acene moieties; namely, the radical centers are shifted from the metal moiety (benzene) to the bridging dinuclear part (anthracene) and then to the acene part (pentacene).

  研究了各种单阳离子二钌（对二乙炔）二基配合物的电荷离域。自由基中心的分布取决于并苯部分；即，自由基中心从金属部分（苯）转移到桥联双核部分（蒽），然后转移到并苯部分（并五苯）。
• Electronic effects of conjugated aryl groups on the properties and reactivities of di(arylethynyl)tetracenes
  作者：Yu Yan、Valentina Brega、Manuel M. Pina、Samuel W. Thomas

  DOI：10.1039/d3ob01601c

  日期：——

  and reactivity with singlet oxygen for eight 5,12-di(arylethynyl)tetracenes. The fluorescence spectra of these tetracenes span approximately 100 nm, while their observed rate constants for reaction with singlet oxygen correlates strongly with the HOMO level, spanning one order of magnitude. They are also amenable to fluorescent materials that respond ratiometrically to singlet oxygen. Therefore, electronic

  并苯的光化学氧化可能对其光电应用（例如单线态裂变和有机晶体管）带来挑战。同时，这些反应构成了许多1 O 2发光传感方案的基础。虽然二乙炔基取代可以说是控制氧化并提高长并苯的溶解度和可加工性的各种取代策略中最广泛采用的，但炔基之间的差异对长并苯的关键性质的影响程度仍然很大程度上未知。因此，本报告描述了各种芳烃和杂芳烃对八种 5,12-二（芳基乙炔基）并四苯的电子结构、光学性质以及与单线态氧的反应性的影响。这些并四苯的荧光光谱跨度约为 100 nm，而观察到的与单线态氧反应的速率常数与 HOMO 能级密切相关，跨越一个数量级。它们还适用于对单线态氧成比例响应的荧光材料。因此，直接与乙炔缀合的基团的电子效应为合理的并苯设计提供了有用的化学空间。
• Resistance to Unwanted Photo-Oxidation of Multi-Acene Molecules
  作者：Yu Yan、Zachary A. Lamport、Ioannis Kymissis、Samuel W. Thomas

  DOI：10.1021/acs.joc.0c01890

  日期：2020.10.2

  Although long acenes remain a key class of pi-conjugated molecules for numerous applications, photoinduced oxidation upon exposure of the acene to light, often through sensitization of O-1(2), is an important reaction requiring mitigation for most applications. In response to this ongoing challenge, this paper presents a series of four new diarylethynyl-substituted long acenes-three tetracenes and one anthradithiophene-in which the arylene pendants are either benzene, naphthalene, or anthracene. UV/vis and fluorescence spectroscopy reveals that the anthracene-substituted derivatives fluoresce poorly (Phi < 0.01). Although all four long acenes react with O-1(2) at expected rates when an external photosensitizer is included and show the expected changes in fluorescence to accompany these reactions, the anthracene-substituted derivatives resist direct photoinduced oxidation. Through a combination of mechanistic experiments, we conclude that rapid nonradiative decay of the anthracene-substituted derivatives, perhaps because of inter-arene torsions that emerge in theoretical geometry optimizations, makes these compounds poor photosensitizers for O-1(2) or other reactive oxygen species. This discovery opens new design possibilities for extended acene structures with improved photochemical stability.
• Gold(I) and Platinum(II) Tetracenes and Tetracenyldiacetylides: Structural and Fluorescence Color Changes Induced by σ-Metalation
  作者：Minh-Hai Nguyen、John H. K. Yip

  DOI：10.1021/om100046h

  日期：2010.6.14

  sigma-Metalation of tetracene can change the emission color of and introduce new structural dimensionality to the organic chromophore. Two synthetic entries to sigma-metallotetracenes have been explored, leading to emissive mononuclear (Ph3PAuI)-tetracene (1) and cis-[Br(Et3P)(2)Pt-II]-tetracene (2) and binuclear (R3PAu(I))(2)-tetracenyldiacetylide (R = Ph (4), Me (5)) and trans-[I(Et3P)(2)Pt-II](2)-tetracenyldiacetylide (6). Metalation can lower the emission energy of tetracene up to 0.53 eV. The X(Et3P)(2)Pt-II group (X = Br, I) has stronger perturbations on the tetracenyl ring than the R3PAu(I) group. sigma-Metalation also leads to different crystal packing of the complexes and thus arrangements of the tetracenyl rings. Aurophilic attraction operates in 5, leading to self-assembly of the molecules into a novel honeycomb structure composed of helical Au-I chains. In contrast to the other complexes, the crystal of 5 is not emissive, possibly due to efficient exciton delocalization.