p-tert-butylthiacalix[4]arene | 288302-14-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚类
• 英文名称: p-tert-butylthiacalix[4]arene
• 英文别名: 5,11,17,23-Tetratert-butylpentacyclo[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-25,26,27,28-tetrathiol
• CAS: 288302-14-7
• 化学式: C₄₄H₅₆S₄
• 分子量: 713.193
• InChiKey: DTAMDUDNIIJSNM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15
• 重原子数：
  48
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  4
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  mercury(II) diacetate 、 p-tert-butylthiacalix[4]arene 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Exoditopic受体I：合成和结构研究上p -叔-butyltetramercaptocalix [4]芳烃和其汞配合物

  摘要：

  的汞（反应II）乙酸乙酯用的1,3-交替构象p -叔-butyltetramercaptocalix [4]芳烃，通过高效率的合成从开始获得p -叔-butylcalix [4]芳烃，通向双核配合物中两个汞离子都线性配位到两个芳硫醇酯基团上

  DOI：

  10.1039/c39940001579
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 在 barium dihydroxide 、 lithium aluminium tetrahydride 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 65.5h， 生成 p-tert-butylthiacalix[4]arene
  参考文献：
  名称：

  Syntheses and Conformations of the p-tert-Butylcalix[4]arenethiols

  摘要：

  The reaction of dimethyl(thiocarbamoyl) chloride with p-tert-butylcalix[4]arene under various conditions yields mixtures from which most of the conformers of the mono-, bis-, tris-, and tetrakis(dimethyl(thiocarbamoyl))oxy compounds have been isolated and purified. Thermal rearrangement of these compounds produces the (dimethylcarbamoyl)thio compounds which, upon reduction with LiAlH4, afford the tetrathiol 14, the trithiol 16, the 1,3-dithiol 21, and the monothiol24. X-ray crystallographic structure determinations and variable-temperature H-1 NMR studies show that the tetrathiol exists as an immobile 1,3-alternate conformer, the trithiol as a semimobile partial cone/1,3-alternate conformer, the 1,3-dithiol as a mobile flattened cone conformer; and the monothiol as a mobile cone conformer. Although the tetrakis(( dimethylcarbamoyl)thio) compound exists in three noninterconverting forms comprising the 1,2-alternate 13, partial cone 18, and 1,3-alternate 19 conformers, all three yield the same tetrathiol 14 upon reduction. Similarly, the syn 22 and anti 20 conformers of the 1,3-bis((dimethylcarbamoyl)thio) compound yield the same dithiol 21. Molecular mechanics calculations for each of the conformers of the mono-, 1,3-di-, tri-, and tetrathiols show general agreement with the X-ray data.

  DOI：

  10.1021/jo00131a014

文献信息

• Calixarene-Based Nanoscale Coordination Cages
  作者：Mei Liu、Wuping Liao、Chunhua Hu、Shangchao Du、Hongjie Zhang

  DOI：10.1002/anie.201106732

  日期：2012.2.13

  Molecular shuttlecocks: The introduction of tripodal ternary acids (red; see picture) to the cobalt/calixarene (green) systems led to the formation of four unprecedented calixarene‐based nanoscale coordination cages through a [6+8] condensation. The overall periphery diameters of the nanocages ranged from 3.3 to 4.7 nm, and there were two sizes for the internal cavities (1.1 and 1.7 nm).

  分子shuttle：将三脚架三元酸（红色；参见图片）引入到钴/杯芳烃（绿色）系统中，导致通过[6 + 8]缩合反应形成了四个前所未有的以杯芳烃为基础的纳米级配位笼。纳米笼的总外周直径在3.3至4.7 nm范围内，内腔有两种尺寸（1.1和1.7 nm）。
• pH-dependent formation of different coordination cages based on Co₄-TC4A secondary building units and bridging ligands
  作者：Xinxin Hang、Shentang Wang、Xiaofei Zhu、Haitao Han、Wuping Liao

  DOI：10.1039/c6ce00028b

  日期：——

  Two kinds of calixarene-based metal–organic coordination cages were obtained at different pH values despite using the same bridging ligand, either 5-(pyridin-3-yl)isophthalic acid (L1) or 5-(5-fluoropyridin-3-yl)isophthalic acid (L2), namely, [Co4(TC4A)Cl]4(Ln)4(HCOO)4(H2O)4]}·26DMF (CIAC-117 and CIAC-119) and H4[Co4(TC4A)Cl]4(Ln)8}·18CH3OH·33DMA (CIAC-118 and CIAC-120), where TC4A represents deprotonated p-tert-butylthiacalix[4]arene, and DMF and DMA represent N,N-dimethylformamide and N,N-dimethylacetamide, respectively. Tetrahedral coordination cages (CIAC-117 and CIAC-119) with shuttlecock-like Co4-TC4A secondary building units (SBUs) as the vertices and L1 and L2 as the three-connected linkers were prepared in the presence of tetramethylammonium hydroxide, while truncated octahedral coordination cages (CIAC-118 and CIAC-120) with L1 and L2 as the two-connected linkers were generated upon the addition of HCl. For CIAC-117, two types of activation methods, solvent exchange-heating and direct heating, were used to investigate the removal of guest molecules in the structure. N2 adsorption properties of activated samples were studied. Moreover, selective dye sorption of CIAC-120 was investigated.

  尽管使用相同的桥联配体5-(吡啶-3-基)间苯二甲酸(L1)或5-(5-氟吡啶-3-基)，但在不同的pH值下获得了两种基于杯芳烃的金属有机配位笼)间苯二甲酸(L2)，即[Co4(TC4A)Cl]4(Ln)4(HCOO)4(H2O)4]}·26DMF （CIAC-117 和 CIAC-119）和 H4[Co4(TC4A)Cl]4(Ln)8}·18CH3OH·33DMA（CIAC-118 和 CIAC-120），其中 TC4A 代表去质子化的对叔丁基硫杂环[4 ]芳烃，DMF和DMA分别表示N，N-二甲基甲酰胺和N，N-二甲基乙酰胺。在四甲基氢氧化铵存在下制备了以羽毛球状Co4-TC4A二级结构单元（SBU）为顶点、L1和L2为三连接体的四面体配位笼（CIAC-117和CIAC-119），而截角八面体协调笼（CIAC-118 和 CIAC-120），L1 和 L2 作为双连接连接器添加 HCl 后生成。对于CIAC-117，采用溶剂交换加热和直接加热两种活化方法来研究结构中客体分子的去除。研究了活化样品的N2吸附性能。此外，还研究了 CIAC-120 的选择性染料吸附。
• The stability enhancement factor beyond eight-electron shell closure in thiacalix[4]arene-protected silver clusters
  作者：Zong-Jie Guan、Feng Hu、Shang-Fu Yuan、Zi-Ang Nan、Yu-Mei Lin、Quan-Ming Wang

  DOI：10.1039/c8sc03756f

  日期：——

  peripheral silver atoms. Surrounding protection is provided by four kinds of ligands, including three BTCA, nine tBuCC, four tfa, and three methanol solvent ligands. It was found that the Ag5@BTCA μ5-coordination motif of thiacalixarene is critical for high stability of the title clusters, and extra stability enhancement can be achieved by doping a gold atom at the center of the silver cluster. This work

  我们报告了两个 34 原子金属纳米团簇的合成和结构，即 [Ag 34 (BTCA) 3 (C CBu t ) 9 (tfa) 4 (CH 3 OH) 3 ]SbF 6和 [AuAg 33 (BTCA) 3 ( C CBu t ) 9 (tfa) 4 (CH 3 OH) 3 ]SbF 6，其中 H 4 BTCA 是对叔叔-丁基噻杯[4]芳烃和tfa是三氟乙酸酯。它们的组成和结构已通过单晶 X 射线结构分析和 ESI-MS 确定。阳离子簇由一个中心二十面体 M@Ag 12（M = Ag 或 Au）核心组成，核心被 21 个外围银原子包围。周围保护由四种配体提供，包括三种BTCA、九种t BuC 、四种tfa和三种甲醇溶剂配体。发现 Ag 5 @BTCA μ 5-噻杯芳烃的配位基序对于标题簇的高稳定性至关重要，并且可以通过在银簇中心掺杂金原子来实现额外的稳定性增强。这项工作表明，除了电子和几何因
• Toroidal moment and dynamical control in luminescent 1D and 3D terbium calixarene compounds
  作者：Hao Wang、Zhenhua Zhu、Léo La Droitte、Wuping Liao、Olivier Cador、Boris Le Guennic、Jinkui Tang

  DOI：10.1039/d3sc00541k

  日期：——

  Tb(III)–calixarene aggregates with architectures of 1D chain (1) and 3D network (2) both containing the square Tb4 unit have been prepared. Their SMT characteristics deriving from the toroidal arrangement of the local magnetic anisotropy axes of Tb(III) ions in the Tb4 unit have been investigated experimentally with the support of ab initio calculations. To the best of our knowledge, 2 is the first covalently

  无机（原子基）铁磁材料可以自发产生环形力矩，打破时间反转和空间反转对称性，引起了固态化学和物理学的高度关注。在分子磁性领域，它也可以在通常具有轮状拓扑结构的镧系元素（Ln）金属有机配合物中实现。这种配合物被称为单分子环面（SMT），在自旋手性量子位和磁电耦合方面呈现出独特的优势。然而，迄今为止，SMT的合成策略仍然难以捉摸，共价键合的三维（3D）扩展SMT迄今尚未合成。在这里，两个发光的 Tb( III )-杯芳烃聚集在一起，具有一维链的结构 ( 1）和3D网络（2）均包含方形Tb 4单元，已制备完毕。它们的 SMT 特性源自Tb 4单元中 Tb( III )离子局部磁各向异性轴的环形排列，并在从头计算的支持下进行了实验研究。据我们所知，2是第一个共价键合的 3D SMT 聚合物。值得注意的是，SMT 行为的溶剂化开关也首次通过1的去溶剂化和溶剂化过程实现。