syn-1,3-bis-[(5-methyl-2,2'-bipyridine-5'-yl)methyl]-p-tert-calix[4]arene | 158750-23-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: syn-1,3-bis-[(5-methyl-2,2'-bipyridine-5'-yl)methyl]-p-tert-calix[4]arene
• 英文别名: 5,11,17,23-Tetratert-butyl-26,28-bis[[6-(5-methylpyridin-2-yl)pyridin-3-yl]methoxy]pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene-25,27-diol
• CAS: 158750-23-3；184851-04-5
• 化学式: C₆₈H₇₆N₄O₄
• 分子量: 1013.38
• InChiKey: VQHQGZKUPZELHM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.4
• 重原子数：
  76
• 可旋转键数：
  12
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  111
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1-(3-溴丙基)吡咯 、 syn-1,3-bis-[(5-methyl-2,2'-bipyridine-5'-yl)methyl]-p-tert-calix[4]arene 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以43%的产率得到5,11,17,23-Tetra(tert-butyl)-26,28-bis(5-methyl-2,2'-bipyridine-5'-methoxy)-25,27-bis(3-(pyrrol-1-yl)propoxy)calix[4]arene
  参考文献：
  名称：

  Calix[4]Arene Podands and Barrelands Incorporating 2,2″-Bipyridine Moieties and Their Lanthanide Complexes: Luminescence Properties

  摘要：

  AbstractA new family of cone‐shaped podands and barrel‐shaped cryptands based on calix[4]arenes incorporating 5,5′‐substituted 2,2′‐bipyridine subunits were prepared and characterized. The Eu3+ and Tb3+ complexes of the podands bearing two, three, or four bipyridine chromophores could be isolated. High molar absorption coefficients (εmax = 39 600M−1 cm−1 for Eu4 and 26 700M−1 cm−1 for Eu3) and high metal luminescence quantum yields (16% for Eu4 and 15% for Eu3) were obtained. Molecular dynamics simulations on Eu4 showed that the bipyridine arms wrap around the lanthanide cation, efficiently shielding the cation from solvent molecules. In the presence of chloride counter‐ions the fourth bipyridine arms does not coordinate the lanthanide ion. Ligands bearing two bipyridine units and two additional functional groups—ethyl butyrate or N‐propylpyrrole—did not give stable lanthanide complexes. The barre‐land containing two calix[4]arene moieties and four bipyridine groups did not form complexes with lanthanide ions, most probably because of the rigidity of the ligand.

  DOI：

  10.1002/chem.19970031114
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 、 2-[5-(溴甲基)吡啶-2-基]-5-甲基吡啶 在 sodium carbonate 作用下， 以78%的产率得到syn-1,3-bis-[(5-methyl-2,2'-bipyridine-5'-yl)methyl]-p-tert-calix[4]arene
  参考文献：
  名称：

  基于5,5'-取代的2,2'-联吡啶亚基的杯杯芳烃[4]-足和桶形杯杯芳烃[4] -cryptands

  摘要：

  新颖的合成和初步镧系元素络合研究顺-1,3-双- [（5-甲基-2,2'-联吡啶-5'-基）甲基] -对-叔-calix [4]芳烃大号3和四[[（5-甲基-2,2'-联吡啶-5'-基）甲基]-对-叔-杯[4]芳烃L 4链烷和新的双[[（2,2'-联吡啶-5， 5'-二基）二甲基]-双-对-叔杯[4]芳烃L 5和四-[（2,2'-联吡啶-5,5'-二基）二甲基]-双-对叔-杯描述了具有桶形结构的[4]芳烃L 6穴状配体。

  DOI：

  10.1016/s0040-4039(00)73416-2

文献信息

• Nitroxo spin-labelled calix[4]arene podands and cryptands: Allosteric regulation of spin-spin exchange interaction
  作者：Gilles Ulrich、Philippe Turek、Raymond Ziessel

  DOI：10.1016/s0040-4039(96)02042-4

  日期：1996.11

  Hybrid calix[4]arene podands and ctyptands, each bearing two or four stable nitronyl-nitroxide radicals and two bipyridine subunits, exhibit through-space exchange interaction, the magnitude of which can be modulated by coordination of ZM(2+) cations at the bipyridine sites. Copyright (C) 1996 Elsevier Science Ltd
• Conformational Control of Intramolecular Electron Transfer in Calix[4]diquinones and Their Cationic Complexes
  作者：Anthony Harriman、Muriel Hissler、Pierre Jost、Georges Wipff、Raymond Ziessel

  DOI：10.1021/ja982786v

  日期：1999.1.1

  The synthesis is described of a photoactive molecular dyad comprising a luminescent ruthenium(II) tris(2,2'-bipyridyl) fragment covalently attached, via a methylene bridge, to a calix[4]arene receptor in which two of the four walls are benzoquinone functions. A distribution of interconverting conformers is expected for the calix[4]arene platform, including cone, partial cone, and 1,3-alternated forms, according to molecular dynamics simulations and NMR studies. Luminescence from the metal complex is quenched because of light-induced electron transfer from the triplet state to a nearby quinone. The MD simulations indicate that the redox-active subunits approach within orbital contact of each other and that the noncone conformations adopt coparallel arrangements of the redox partners that appear to be highly favorable for electron transfer. Cations, such as barium(II), are held at the lower rim of the receptor by coordination to the four O atoms and by two N atoms provided by an ancillary 2,2'-bipyridine that is appended to the receptor. Cation complexation increases slightly the thermodynamic driving force for light-induced electron transfer but restores luminescence from the ruthenium(II) tris(2,2'-bipyridyl) fragment. This apparent contradiction is explained in terms of the cation inducing a major structural modification of the supermolecule. Both MD and NMR studies indicate that the cation forces the luminophore away from the quinone and, by favoring the cone conformation of the calix[4]arene, destabilizes cofacial orientations between closely spaced reactants. Consequently, the system functions as a sensitive photoionic detector.