16,17-didehydro-5,11-dihydro-7H-dibenzo[g,k][1,5]dioxacyclotridecyne-7,9(8H)-dione | 1421837-02-6

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 16,17-didehydro-5,11-dihydro-7H-dibenzo[g,k][1,5]dioxacyclotridecyne-7,9(8H)-dione
• 英文别名: 11,15-Dioxatricyclo[15.4.0.04,9]henicosa-1(21),4,6,8,17,19-hexaen-2-yne-12,14-dione；11,15-dioxatricyclo[15.4.0.04,9]henicosa-1(21),4,6,8,17,19-hexaen-2-yne-12,14-dione
• CAS: 1421837-02-6
• 化学式: C₁₉H₁₄O₄
• 分子量: 306.318
• InChiKey: RKHGHCPMSCIKDE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.16
• 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：

  16,17-didehydro-5,11-dihydro-7H-dibenzo[g,k][1,5]dioxacyclotridecyne-7,9(8H)-dione 、 碘甲烷 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 48.5h， 以56%的产率得到13,13-Dimethyl-11,15-dioxatricyclo[15.4.0.04,9]henicosa-1(21),4,6,8,17,19-hexaen-2-yne-12,14-dione
  参考文献：
  名称：

  Bridged Tolanes: A Twisted Tale

  摘要：

  The rotational motion of tolanes along their acetylene axis is not fully understood. What happens to the optical and electronic properties if the tolane backbone is forced into a twisted conformation? Several tethers were investigated to obtain tolanophanes, fixing the torsion angle of the two phenyl rings. X-ray crystal structures revealed tether-specific torsion angles in the solid state. The absorption, emission, and excitation spectra were recorded. Twisted tethered tolane conformers showed blue-shifted absorption; emission spectra were all torsionally independent and identical. The tethered tolanes were embedded in a rigid matrix by freezing to 77 K; well-resolved emission spectra were recorded for planar tolanes, but for twisted systems unexpectedly long-lived phosphorescence was observed. How is this triplet emission explained? Quantum chemical calculations (TDDFT/cam-B3LYP/6-31G*) of the unsubstituted tolane showed that intersystem crossing (ISC) is favored with large spin-orbit coupling, which occurs when the molecular orbitals are orthogonal to each other; this is the case at the crossing of S-1/T-7. Also, a small energy difference between singlet and triplet states is required; we found that ISC can favorably take place at four crossings: S-1/T-6, S-1/T-7, S-1/T-8,T-9, S-1/T-10.

  DOI：

  10.1021/jo5010235
• 作为产物：
  描述：

  2-碘苄醇 在 哌啶 、 copper(l) iodide 、 四(三苯基膦)钯 、 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 16.0h， 生成 16,17-didehydro-5,11-dihydro-7H-dibenzo[g,k][1,5]dioxacyclotridecyne-7,9(8H)-dione
  参考文献：
  名称：

  Twisted Tethered Tolanes：77 K 下意外的长寿命磷光

  摘要：

  影响共轭体系内的通讯如二苯乙炔是分子电子学中的一个具有挑战性的课题。已知扭曲的 tolanes 的一些例子，其中通过空间阻碍在固态下实现了高扭曲。间隔系统的插入是定制旋转的另一种方式。仅存在少数此类系留托车道的示例，并且它们都具有小扭曲角 (<35°)。我们报告了含有丙二酰系链的 tolanophanes，其扭曲角达到了近 80°。记录了长寿命磷光（77 K 下 4 秒），并进行了量子化学计算以确认实验结果。

  DOI：

  10.1021/ja400416r

文献信息

• Synthesis and Properties of Functional Twisted Tolanes
  作者：Yury Kozhemyakin、Andreas Kretzschmar、Maximilian Krämer、Frank Rominger、Andreas Dreuw、Uwe H. F. Bunz

  DOI：10.1002/chem.201701519

  日期：2017.7.21

  and optical properties of several novel fluorescent and/or phosphorescent bridged tolanes (tolanophanes) are reported and their optical and structural properties are investigated. Specifically, diiodinated and bisalkynylated tolanophanes were obtained, and characterized by spectroscopy and computational methods. They represent attractive building blocks for novel polymers and emissive solid‐state materials

  报道了几种新颖的荧光和/或磷光桥连的戊二烯（tolanophanes）的合成和光学性质，并研究了它们的光学和结构性质。具体而言，获得了二碘化和双烷基化的tolanophanes，并通过光谱法和计算方法对其进行了表征。它们代表了新型聚合物和发光固态材料的有吸引力的构建基块。
• Twisted Tethered Tolanes: Unanticipated Long-Lived Phosphorescence at 77 K
  作者：Sebastian Menning、Maximilian Krämer、Benjamin A. Coombs、Frank Rominger、Andrew Beeby、Andreas Dreuw、Uwe H. F. Bunz

  DOI：10.1021/ja400416r

  日期：2013.2.13

  tethered tolanes exist, and they all suffer from small twist angles (<35°). We report on tolanophanes containing a malonyl tether, where twist angles of almost 80° were reached. Long-lived phosphorescence (4 s at 77 K) was recorded, and quantum-chemical calculations were performed to confirm the experimental results.

  影响共轭体系内的通讯如二苯乙炔是分子电子学中的一个具有挑战性的课题。已知扭曲的 tolanes 的一些例子，其中通过空间阻碍在固态下实现了高扭曲。间隔系统的插入是定制旋转的另一种方式。仅存在少数此类系留托车道的示例，并且它们都具有小扭曲角 (<35°)。我们报告了含有丙二酰系链的 tolanophanes，其扭曲角达到了近 80°。记录了长寿命磷光（77 K 下 4 秒），并进行了量子化学计算以确认实验结果。
• Bridged Tolanes: A Twisted Tale
  作者：Sebastian Menning、Maximilian Krämer、Andrew Duckworth、Frank Rominger、Andrew Beeby、Andreas Dreuw、Uwe H. F. Bunz

  DOI：10.1021/jo5010235

  日期：2014.7.18

  The rotational motion of tolanes along their acetylene axis is not fully understood. What happens to the optical and electronic properties if the tolane backbone is forced into a twisted conformation? Several tethers were investigated to obtain tolanophanes, fixing the torsion angle of the two phenyl rings. X-ray crystal structures revealed tether-specific torsion angles in the solid state. The absorption, emission, and excitation spectra were recorded. Twisted tethered tolane conformers showed blue-shifted absorption; emission spectra were all torsionally independent and identical. The tethered tolanes were embedded in a rigid matrix by freezing to 77 K; well-resolved emission spectra were recorded for planar tolanes, but for twisted systems unexpectedly long-lived phosphorescence was observed. How is this triplet emission explained? Quantum chemical calculations (TDDFT/cam-B3LYP/6-31G*) of the unsubstituted tolane showed that intersystem crossing (ISC) is favored with large spin-orbit coupling, which occurs when the molecular orbitals are orthogonal to each other; this is the case at the crossing of S-1/T-7. Also, a small energy difference between singlet and triplet states is required; we found that ISC can favorably take place at four crossings: S-1/T-6, S-1/T-7, S-1/T-8,T-9, S-1/T-10.