(4,7,12,15)-tetra(diethylphosphonatemethyl)[2.2]paracyclophane | 433719-59-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: (4,7,12,15)-tetra(diethylphosphonatemethyl)[2.2]paracyclophane
• 英文别名: 4,7,12,15-tetra-(diethoxyphosphorylmethyl)-[2.2]paracyclophane；4,7,12,15-tetra[(methyl)diethylphosphonate][2.2]paracyclophane；4,7,12,15-tetra(diethylphosphonatemethyl)-[2.2]paracyclophane；4,7,12,15-tetra-(diethylphosphonatemethyl)paracyclophane；5,11,13,15-Tetrakis(diethoxyphosphorylmethyl)tricyclo[8.2.2.24,7]hexadeca-1(12),4(16),5,7(15),10,13-hexaene
• CAS: 433719-59-6
• 化学式: C₃₆H₆₀O₁₂P₄
• 分子量: 808.76
• InChiKey: GURAKFTXJZNXCZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  52
• 可旋转键数：
  24
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  142
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (4,7,12,15)-tetra(diethylphosphonatemethyl)[2.2]paracyclophane 在 potassium tert-butylate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 4,7-bis(4'-dihexylaminostyryl)-12,15-bis(4''-nitrostyryl)[2.2]-paracyclophane
  参考文献：
  名称：

  含有供体和受体基团的 4,7,12,15-[2.2] 对环芳烷的合成、表征和光谱：取代模式对空间电荷转移的影响

  摘要：

  本文报道了4,7,12,15-四(4'-二己基氨基苯乙烯基)[2.2]对环烷(1), 4-(4'-二己基氨基苯乙烯基)-7,12,15-三(4''-硝基苯乙烯基)[2.2] 对环烷 (2), 4,7-双(4'-二己基氨基苯乙烯基)-12,15-双(4''-硝基苯乙烯基)-[2.2] 对环烷 (3), 4,7,12-tris (4'-二己基氨基苯乙烯基)-15-(4''-硝基苯乙烯基)[2.2]对环烷 (4), 4,15-双(4'-二己基氨基苯乙烯基)-7,12-双(4''-硝基苯乙烯基)[2.2 ]对环烷(5)和4,12-双(4'-二己基氨基苯乙烯基)-7,15-双(4''-硝基苯乙烯基)[2.2]对环烷(6)。这些分子代表将含有供体和受体基团的二苯乙烯基苯发色团通过 [2.2] 对环烷 (pCp) 桥结合在一起的不同组合。X 射线衍射研究表明，1 和 3 的晶格排列与母发色团 1,4-双(4'二己基氨基苯乙烯基)苯

  DOI：

  10.1021/ja0121383
• 作为产物：
  描述：

  (4,7,12,15)-tetra α-bromomethyl[2.2]paracyclophane 、 亚磷酸三乙酯 反应 2.0h， 以98%的产率得到(4,7,12,15)-tetra(diethylphosphonatemethyl)[2.2]paracyclophane
  参考文献：
  名称：

  含有供体和受体基团的 4,7,12,15-[2.2] 对环芳烷的合成、表征和光谱：取代模式对空间电荷转移的影响

  摘要：

  本文报道了4,7,12,15-四(4'-二己基氨基苯乙烯基)[2.2]对环烷(1), 4-(4'-二己基氨基苯乙烯基)-7,12,15-三(4''-硝基苯乙烯基)[2.2] 对环烷 (2), 4,7-双(4'-二己基氨基苯乙烯基)-12,15-双(4''-硝基苯乙烯基)-[2.2] 对环烷 (3), 4,7,12-tris (4'-二己基氨基苯乙烯基)-15-(4''-硝基苯乙烯基)[2.2]对环烷 (4), 4,15-双(4'-二己基氨基苯乙烯基)-7,12-双(4''-硝基苯乙烯基)[2.2 ]对环烷(5)和4,12-双(4'-二己基氨基苯乙烯基)-7,15-双(4''-硝基苯乙烯基)[2.2]对环烷(6)。这些分子代表将含有供体和受体基团的二苯乙烯基苯发色团通过 [2.2] 对环烷 (pCp) 桥结合在一起的不同组合。X 射线衍射研究表明，1 和 3 的晶格排列与母发色团 1,4-双(4'二己基氨基苯乙烯基)苯

  DOI：

  10.1021/ja0121383

文献信息

• Two-Photon Absorption in Three-Dimensional Chromophores Based on [2.2]-Paracyclophane
  作者：Glenn P. Bartholomew、Mariacristina Rumi、Stephanie J. K. Pond、Joseph W. Perry、Sergei Tretiak、Guillermo C. Bazan

  DOI：10.1021/ja038743i

  日期：2004.9.1

  and bis(1,4)-(4' '-(4'-dihexylaminostyryl)styryl)benzene (5R) were also synthesized to reveal the properties of the "monomeric" counterparts. The two-photon absorption cross sections were determined by the two-photon induced fluorescence method using both femtosecond and nanosecond pulsed lasers as excitation sources. While there is a red shift in the linear absorption spectra when going from the "monomer"

  合成了一系列由 [2.2] 对环芳烃核心结合在一起的 α,omega-bis 供体取代的低聚亚苯基亚乙烯基二聚体，以探测重复单元的数量和通过空间离域如何影响双光子吸收截面。具体而言，对环烷分子是四(4,7,12,15)-(4'-二己基氨基苯乙烯基)[2.2]对环烷(3R(D))，四(4,7,12,15)-(4''- (4'-二己基氨基苯乙烯基)苯乙烯基)[2.2]对环烷(5R(D))和四(4,7,12,15)-(4'"-(4''-(4'-二己基氨基苯乙烯基)苯乙烯基)苯乙烯基)[2.2] 对环芳烷 (7R(D)). 化合物双 (1,4)-(4'-二己基氨基苯乙烯基)苯 (3R) 和双 (1,4)-(4''-(4'-二己基氨基苯乙烯基)还合成了苯乙烯基)苯 (5R) 以揭示“单体”对应物的特性。双光子吸收截面通过使用飞秒和纳秒脉冲激光器作为激发源的双光子诱导荧光法测定。当从“单体”发色团到对环芳烃“二聚体”（即
• α,ω-Bis(thioacetyl)oligophenylenevinylene Chromophores from Thioanisol Precursors
  作者：Dwight S. Seferos、David A. Banach、Norma A. Alcantar、Jacob N. Israelachvili、Guillermo C. Bazan

  DOI：10.1021/jo035664g

  日期：2004.2.1

  The selective cleavage of arylmethyl thioethers provides a convenient protocol for the synthesis of all-E isomers of α,ω-bis(thioacetyl)oligophenyenevinylene molecules (OPVs). The S-methyl group is tolerant of Wittig-type and Heck-type reactions for forming OPV structures and can be converted to the S-acetyl group by treatment with sodium thiomethoxide and acetyl chloride. The thermal conditions of

  芳甲基硫醚的选择性切割提供了一个方便的方案用于合成所有- Ë α的同分异构体，ω -双（硫代乙酰基）oligophenyenevinylene分子（OPV中）。该小号-甲基组是维蒂希型的耐受性和用于形成OPV结构的Heck型反应，可以转化为小号通过与甲硫醇钠和乙酰氯处理乙酰基。脱保护/重新保护步骤的热条件同时异构化共轭发色团向全- ë异构体，与起始烯烃的立体化学无关。该方法已用于多种线性和[2.2]对环环烷烃的OPV，这些均已通过电化学和光谱技术进行了表征。另外，这些S-乙酰基封端的OPV在金表面上自组装。包含这些分子的单分子层通过水接触角测量，椭圆偏振法和X射线光电子能谱进行了表征。
• Paracyclophane molecules for two-photon absorption applications
  申请人：Bazan C. Guillermo

  公开号：US20060208235A1

  公开（公告）日：2006-09-21

  Chromophores having two-photon or other multi-photon absorptivity. The chromophores are based on a structure of four stilbenoid groups attached to a paracyclophane core, where each stilbenoid group comprises a nitrogen-containing organic group attached by its nitrogen atom to a stilbenoid arm. In particular embodiments, at least one of the stilbenoid groups includes a sulfonium, ammonium, selenium, iodonium or phosphonium moiety. The chromophores have utility as photo-polymerization initiators and two-photon fluorophores for biological imaging.

  具有双光子或其他多光子吸收性的色素团。这些色素团基于连接到对环芳烃核心的四个苯乙烯基团的结构，其中每个苯乙烯基团包括一个含氮有机基团，通过其氮原子连接到苯乙烯基团。在特定实施例中，至少一个苯乙烯基团包括硫鎓、铵鎓、硒鎓、碘鎓或磷鎓基团。这些色素团可用作光聚合引发剂和生物成像的双光子荧光团。
• Solvatochromism of Distyrylbenzene Pairs Bound Together by [2.2]Paracyclophane:  Evidence for a Polarizable “Through-Space” Delocalized State
  作者：Janice W. Hong、Han Young Woo、Bin Liu、Guillermo C. Bazan

  DOI：10.1021/ja044326+

  日期：2005.5.25

  compounds were designed and synthesized to examine how through-space and through-bond electron delocalization respond to solvent effects. The general strategy involves the study of "dimers" of the distyrylbenzene chromophore held in close proximity by the [2.2]paracyclophane core and a systematic dissection of the chromophore into components with through-space and through-bond electronic delocalization. Steady

  设计并合成了一系列化合物，以检查空间和键合电子离域如何响应溶剂效应。一般策略涉及研究由 [2.2] 对环芳核心紧密靠近的二苯乙烯基苯发色团的“二聚体”，以及将发色团系统地分解为具有通过空间和通过键电子离域的组件。一系列溶剂中的稳态和时间分辨荧光光谱显示，当不存在供体取代基时，在极性溶剂中发射状态的发射红移和固有荧光寿命增加。我们提出跨 [2.2] 对环芳烷核心的空间离域在激发态更容易极化，相对于直通键（二苯乙烯基）激发态。当强供体连接到二苯乙烯基苯发色团时，基于二苯乙烯基苯的激发态的电荷转移特性决定了荧光特性。
• Water-Soluble [2.2]Paracyclophane Chromophores with Large Two-Photon Action Cross Sections
  作者：Han Young Woo、Janice W. Hong、Bin Liu、Alexander Mikhailovsky、Dmitry Korystov、Guillermo C. Bazan

  DOI：10.1021/ja0440811

  日期：2005.1.1

  A series of alpha,omega-donor-substituted distyrylbenzene dimers held together by the [2.2]paracyclophane core were designed, synthesized, and characterized. Different substituents were chosen to modulate the strength of the donor nitrogen groups and to allow the molecules to be either neutral and soluble in nonpolar organic solvents or charged and water-soluble. The specific neutral structures are (in order of decreasing donor strength) 4,7,12,15-tetra[N,N-bis(6' '-chlorohexyl)-4'-aminostyryl]-[2.2]paracyclophane (1N), 4,7,12,15-tetra[(N-(6' '-chlorohexyl)carbazol-3'-yl)vinyl]-[2.2]paracyclophane (2N), and 4,7,12,15-tetra[N,N-bis(4' '-(6' ''-chlorohexyl)phenyl)-4'-aminostyryl]-[2.2]paracyclophane (3N). The charged species are 4,7,12,15-tetra[N,N-bis(6' '-(N,N,N-trimethylammonium)hexyl)-4'-aminostyryl]-[2.2]paracyclophane octaiodide (1C), 4,7,12,15-tetra[(N-(6' '-(N,N,N-trimethylammonium)hexyl)carbazol-3'-yl)vinyl]-[2.2]paracyclophane octaiodide (2C), and 4,7,12,15-tetra[N,N-bis(4' '-(6' ''-(N,N,N-trimethylammonium)hexyl)phenyl)-4'-aminostyryl]-[2.2]paracyclophane octaiodide (3C). Two-photon excitation spectra, measured using the two-photon induced fluorescence technique, show in toluene the following trend for the two-photon cross sections (delta): 3N > 2N > 1N. In water the delta values follow the same order, 3C approximately 2C > 1C, but are smaller (approximately one-third). Significantly, the fluorescence quantum yield (eta) in water decreases much more for 1, relative to 2 and 3. The two-photon action cross sections (deltaeta) of 2C and 3C are 294 GM and 359 GM, respectively. These values are among the highest reported thus far. These results show that, to maximize the deltaeta in this class of chromophores, one needs to fine-tune the magnitude of the charge transfer character of the excited state, to minimize fluorescence quenching in polar media.