1,4-bis-(([3-hydroxydiphenyl]-phenylmethyl)ethynyl)phenylene | 1338248-49-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 1,4-bis-(([3-hydroxydiphenyl]-phenylmethyl)ethynyl)phenylene
• 英文别名: 1,4-bis(3-(3-hydroxyphenyl)-3,3-diphenylpropynyl)benzene；3-[3-[4-[3-(3-Hydroxyphenyl)-3,3-diphenylprop-1-ynyl]phenyl]-1,1-diphenylprop-2-ynyl]phenol
• CAS: 1338248-49-9
• 化学式: C₄₈H₃₄O₂
• 分子量: 642.797
• InChiKey: NWBGGLQTGOJKOA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.1
• 重原子数：
  50
• 可旋转键数：
  10
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-bis-(([3-hydroxydiphenyl]-phenylmethyl)ethynyl)phenylene 、 1,10-二溴癸烷 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以46%的产率得到4,4,27,27-Tetraphenyl-10,21-dioxatetracyclo[28.2.2.15,9.122,26]hexatriaconta-1(33),5(36),6,8,22,24,26(35),30(34),31-nonaen-2,28-diyne
  参考文献：
  名称：

  Synthesis of Bridged Molecular Gyroscopes with Closed Topologies: Triple One-Pot Macrocyclization

  摘要：

  We describe the synthesis and characterization of six bridged molecular gyroscopes with m-alkoxy-substituted trityl stators and dialkynylphenylene rotators. All of the bridged molecular gyroscopes were synthesized convergently to form the phenolic stator-rotator framework, while the alkyl and benzophenone bridges were installed in one step by relatively efficient one-pot reactions to form macrocyclic diether or diester linkages. The isolated yield per bond-forming reaction varied from ca. 42% to 80%, with one exception where macrocyclization failed to produce the desired product. The molecular structure and crystal packing of each of the bridged molecular gyroscopes were determined via single crystal X-ray diffraction. Like most molecular gyroscopes with open topologies previously studied, the singly bridged structures pack by interdigitating one trityl stator in one molecule next to the rotator of an adjacent molecule in the lattice. In contrast, the triply bridged molecular gyroscopes were found to pack in lamellar sheets that prevent the rotator-stator interdigitation of adjacent molecules. However, solvent molecules and conformationally flexible bridges tend to fill in the packing volume by collapsing next to the rotator or by extending one of their bridges into the cavity of a neighboring molecule.

  DOI：

  10.1021/jo201513y
• 作为产物：
  描述：

  m-methoxytrityl chloride 在 copper(l) iodide 、 trans-bis(triphenylphosphine)palladium dichloride 、 三溴化硼 、 二异丙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 27.0h， 生成 1,4-bis-(([3-hydroxydiphenyl]-phenylmethyl)ethynyl)phenylene
  参考文献：
  名称：

  Synthesis of Bridged Molecular Gyroscopes with Closed Topologies: Triple One-Pot Macrocyclization

  摘要：

  We describe the synthesis and characterization of six bridged molecular gyroscopes with m-alkoxy-substituted trityl stators and dialkynylphenylene rotators. All of the bridged molecular gyroscopes were synthesized convergently to form the phenolic stator-rotator framework, while the alkyl and benzophenone bridges were installed in one step by relatively efficient one-pot reactions to form macrocyclic diether or diester linkages. The isolated yield per bond-forming reaction varied from ca. 42% to 80%, with one exception where macrocyclization failed to produce the desired product. The molecular structure and crystal packing of each of the bridged molecular gyroscopes were determined via single crystal X-ray diffraction. Like most molecular gyroscopes with open topologies previously studied, the singly bridged structures pack by interdigitating one trityl stator in one molecule next to the rotator of an adjacent molecule in the lattice. In contrast, the triply bridged molecular gyroscopes were found to pack in lamellar sheets that prevent the rotator-stator interdigitation of adjacent molecules. However, solvent molecules and conformationally flexible bridges tend to fill in the packing volume by collapsing next to the rotator or by extending one of their bridges into the cavity of a neighboring molecule.

  DOI：

  10.1021/jo201513y

文献信息

• Fluorescence and Rotational Dynamics of a Crystalline Molecular Rotor Featuring an Aggregation-Induced Emission Fluorophore
  作者：Morgan E. Howe、Miguel A. Garcia-Garibay

  DOI：10.1021/acs.joc.9b01201

  日期：2019.8.2

  tetraphenylethylene (TPE), a fluorophore known to emit with intensities that depend on the rigidity of the medium. We envisioned that an increase in crystal fluidity as a function of increasing temperature would facilitate rotational motion of the DEB while diminishing the fluorescence intensity of the TPE. The aggregation-induced emission of the TPE moiety was confirmed when its fluorescence intensity increased

  最近的研究表明，快速构象运动形式的“晶体流动性”对于晶体中的大振幅旋转运动至关重要。为了探索这一概念，我们设计了一个晶体组件，该组件具有两个与四苯基乙烯（TPE）连接的二乙炔基苯（DEB）分子旋转器，四苯基乙烯（TPE）是一种荧光团，其发射强度取决于介质的刚度。我们预想，随着温度的升高，晶体流动性的增加将有利于DEB的旋转运动，同时减小TPE的荧光强度。当通过向THF溶液中添加水而增加其荧光强度时，证实了TPE部分的聚集诱导的发射。虽然散装固体显示出相对较强的TPE发射，寿命为4±1 ns，在从77 K到298 K的测量之间没有观察到显着变化，表明晶体环境在激发态寿命内的运动受到限制。四极回波证实了这一结论氘标记的样品在198和298 K之间的2 H NMR线形分析显示了微秒状态下的旋转相关时间，表明旋转流动性太慢3个数量级，以至于无法影响荧光发射。
• Crystalline arrays of molecular rotors with TIPS-trityl and phenolic-trityl stators using phenylene, 1,2-difluorophenylene and pyridine rotators
  作者：Rafael Arcos-Ramos、Braulio Rodriguez-Molina、E. Gonzalez-Rodriguez、Pedro I. Ramirez-Montes、Maria Eugenia Ochoa、Rosa Santillan、Norberto Farfán、Miguel A. Garcia-Garibay

  DOI：10.1039/c5ra07422c

  日期：——

  describe the synthesis and solid-state characterization of a series of molecular rotors with tri-isopropylsilyloxy-substituted (TIPS) trityl stators axially linked to 1,4-diethynylphenylene, 3,6-diethynyl-1,2-difluorophenylene and 2,5-diethynylpyridine rotators to produce 1,4-bis[(3,3-diphenyl-3-(3′-(tri-isopropylsilyloxy)-phenyl)-prop-1-yn-1-yl)]benzene (1), 1,4-bis[(3,3-diphenyl-3-(3′-(tri-isoprop

  在这项工作中，我们描述了一系列轴向与1,4-二乙炔基亚苯基，3,6-二乙炔基-1,2-二氟亚苯基连接的三异丙基甲硅烷基氧基取代（TIPS）三苯甲基定子的分子转子的合成和固态表征和2,5-二甲基吡啶吡啶旋转器生产1,4-双[（3,3-二苯基-3-（3'-（三异丙基甲硅烷氧基）-苯基）-丙-1-炔-1-基）]苯（1），1,4-双[（3,3-二苯基-3-（3'-（三异丙基甲硅烷氧基）-苯基）-prop-1-yn-1-yl）]-2,3-二氟苯（2）和2,5-双[（3,3-二苯基-3-（3'-三异丙基甲硅烷氧基）-苯基）-prop-1-yn-1-yl）]吡啶（3）。随后去除TIPS保护基导致它们相应的羟基取代的三苯甲基衍生物（4）和（5）。TIPS和HO取代的定子参与不同的分子间和分子间相互作用（氢键，苯基环抱，CH–H–π相互作用），从而产生同构堆积图案，从而将固态旋转动力学限制为缓慢交换制度。
• Photochromic Molecular Gyroscope with Solid State Rotational States Determined by an Azobenzene Bridge
  作者：Patrick Commins、Miguel A. Garcia-Garibay

  DOI：10.1021/jo402516n

  日期：2014.2.21

  photochemical isomerization, and rotational dynamics of a crystalline molecular gyroscope containing an azobenzene bridge (trans-2) that spans from one end of the stator to other, with the intention of exploring its function as a molecular brake. While single crystal X-ray diffraction analysis of a photochemically inactive dichloromethane solvate was used to confirm the molecular and packing structures of

  我们描述了包含偶氮苯桥（trans - 2）的晶体分子陀螺仪的合成，表征，光化学异构化和旋转动力学，该偶氮苯桥跨越从定子的一端到另一端，以探索其作为分子制动器的功能。虽然使用了光化学非活性二氯甲烷溶剂化物的单晶X射线衍射分析，以确认的分子和包装结构的反式- 2，纳米晶体假多被证明是光活性的，并且它是由粉末X射线衍射（PXRD）分析，扫描电子显微镜和可变温度固态2光异构化前后的1 H NMR。结果表明，与在溶液中观察到的相应值是74％的溶液相比，用λ= 340 nm照射的纳米晶体悬浮液具有34％的顺式异构体达到了光平稳状态。对苯并d 4同位素分子的固态2 H NMR光谱进行线形分析（随温度变化），表明反式2异构体晶体的旋转，平均活化能为4.6±0.6 kcal / mol，前指数因子exp（29.4±1.7）比包含cis- 2的样品快十倍 异构体，其平均活化能较高，为5.1±0.6 kcal
• Synthesis of Bridged Molecular Gyroscopes with Closed Topologies: Triple One-Pot Macrocyclization
  作者：Patrick Commins、Jose E. Nuñez、Miguel A. Garcia-Garibay

  DOI：10.1021/jo201513y

  日期：2011.10.21

  We describe the synthesis and characterization of six bridged molecular gyroscopes with m-alkoxy-substituted trityl stators and dialkynylphenylene rotators. All of the bridged molecular gyroscopes were synthesized convergently to form the phenolic stator-rotator framework, while the alkyl and benzophenone bridges were installed in one step by relatively efficient one-pot reactions to form macrocyclic diether or diester linkages. The isolated yield per bond-forming reaction varied from ca. 42% to 80%, with one exception where macrocyclization failed to produce the desired product. The molecular structure and crystal packing of each of the bridged molecular gyroscopes were determined via single crystal X-ray diffraction. Like most molecular gyroscopes with open topologies previously studied, the singly bridged structures pack by interdigitating one trityl stator in one molecule next to the rotator of an adjacent molecule in the lattice. In contrast, the triply bridged molecular gyroscopes were found to pack in lamellar sheets that prevent the rotator-stator interdigitation of adjacent molecules. However, solvent molecules and conformationally flexible bridges tend to fill in the packing volume by collapsing next to the rotator or by extending one of their bridges into the cavity of a neighboring molecule.