1-(4-iodophenyl)-3,5,7-tris(acetylthiomethyl)adamantane | 1026186-70-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(4-iodophenyl)-3,5,7-tris(acetylthiomethyl)adamantane
• 英文别名: S-[[3,5-bis(acetylsulfanylmethyl)-7-(4-iodophenyl)-1-adamantyl]methyl] ethanethioate
• CAS: 1026186-70-8
• 化学式: C₂₅H₃₁IO₃S₃
• 分子量: 602.622
• InChiKey: HIIIKBDBPWQEEE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  32
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  127
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-(4-iodophenyl)-3,5,7-tris(acetylthiomethyl)adamantane 在 氢氧化钾 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 1.0h， 以86%的产率得到1-(4-iodophenyl)-3,5,7-tris(mercaptomethyl)adamantane
  参考文献：
  名称：

  Rigid Molecular Tripod with an Adamantane Framework and Thiol Legs. Synthesis and Observation of an Ordered Monolayer on Au(111)

  摘要：

  Tripod-shaped trithiols 1-3, containing CH2SH groups at the three bridgehead positions of the adamantane framework and a halogen-containing group [Br (1), p-BrC6H4 (2), or p-IC6H4 (3)] at the fourth bridgehead, were synthesized, and self-assembled monolayers (SAMs) were prepared on atomically flat Au(111) surfaces. The three-point chemisorption of these tripods was confirmed by polarization modulation infrared reflection absorption spectroscopy, which showed the absence of a S-H stretching band. Scanning tunneling microscopy of the SAM of 1 exhibited a hexagonal arrangement of the adsorbed molecule with a lattice constant of 8.7 angstrom. A unidirectionally oriented, head-to-tail array of 1, which allows the close approach of neighboring molecules, is proposed as a reasonable model of the two-dimensional crystal, where the adsorbed sulfur atoms form a quasi-(root 3 x root 3)R30 degrees lattice. The charge of the electrochemical reductive desorption of the SAM of 1 was in good agreement with the expected surface coverage, while the SAMs of 2 and 3 showed somewhat less (ca. 70%) charge. The large negative reduction peak potentials, observed for the SAM of 1, are taken to indicate a tight anchoring of this tripod by three sulfur atoms.

  DOI：

  10.1021/jo051863j
• 作为产物：
  描述：

  1-bromo-3,5,7-tris(hydroxymethyl)adamantane 在 吡啶 、 silver hexafluoroantimonate 、 18-冠醚-6 、 碘 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 四氯化碳 、 二氯甲烷 、 乙腈 为溶剂， 反应 100.0h， 生成 1-(4-iodophenyl)-3,5,7-tris(acetylthiomethyl)adamantane
  参考文献：
  名称：

  Rigid Molecular Tripod with an Adamantane Framework and Thiol Legs. Synthesis and Observation of an Ordered Monolayer on Au(111)

  摘要：

  Tripod-shaped trithiols 1-3, containing CH2SH groups at the three bridgehead positions of the adamantane framework and a halogen-containing group [Br (1), p-BrC6H4 (2), or p-IC6H4 (3)] at the fourth bridgehead, were synthesized, and self-assembled monolayers (SAMs) were prepared on atomically flat Au(111) surfaces. The three-point chemisorption of these tripods was confirmed by polarization modulation infrared reflection absorption spectroscopy, which showed the absence of a S-H stretching band. Scanning tunneling microscopy of the SAM of 1 exhibited a hexagonal arrangement of the adsorbed molecule with a lattice constant of 8.7 angstrom. A unidirectionally oriented, head-to-tail array of 1, which allows the close approach of neighboring molecules, is proposed as a reasonable model of the two-dimensional crystal, where the adsorbed sulfur atoms form a quasi-(root 3 x root 3)R30 degrees lattice. The charge of the electrochemical reductive desorption of the SAM of 1 was in good agreement with the expected surface coverage, while the SAMs of 2 and 3 showed somewhat less (ca. 70%) charge. The large negative reduction peak potentials, observed for the SAM of 1, are taken to indicate a tight anchoring of this tripod by three sulfur atoms.

  DOI：

  10.1021/jo051863j

文献信息

• Electrochemistry of the Self-Assembled Monolayers of Dyads Consisting of Tripod-Shaped Trithiol and Bithiophene on Gold
  作者：Toshikazu Kitagawa、Hiroaki Matsubara、Takao Okazaki、Koichi Komatsu

  DOI：10.3390/molecules190915298

  日期：——

  Self-assembled monolayers (SAMs) of tripod-shaped trithiols, consisting of an adamantane core with three CH2SH legs and a bithiophene group, were prepared on a Au(111) surface. Adsorption in a tripod-like fashion was supported by polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS) of the SAMs, which indicated the absence of free SH groups. Cyclic voltammetry showed an irreversible cathodic wave due to reductive desorption. The SAM also showed an anodic wave due to the single-electron oxidation of the bithiophene moiety without concomitant desorption of the molecules. Although oxidation was irreversible in the absence of a protecting group, it became reversible with the introduction of a terminal phenyl group. The charge of the oxidation was one-third that of the reductive desorption, confirming a three-point adsorption. The surface coverage was ca. 50% of that expected for the anti bithiophene conformation, which suggested that an increase in the surface area per molecule had been caused by the presence of an energetically high-lying syn conformer. In accordance with this, the line shape of the oxidation wave suggested an electrostatic repulsive interaction between neighboring molecules.

  这项研究描述了在Au(111)表面上制备的三脚架状三硫醇自组装单分子层(SAMs)。主要研究结果如下: 1. 这种三脚架分子由金刚烷核心、三个CH2SH腿和一个联噻吩基团组成。 2. 通过偏振调制-红外反射吸收光谱(PM-IRRAS)证实了三脚架式吸附,因为没有检测到游离的SH基团。 3. 循环伏安法显示: - 出现不可逆的阴极波,源于还原脱附 - 出现阳极波,源于联噻吩部分的单电子氧化,但分子不会脱附 - 没有保护基团时氧化是不可逆的,加入末端苯基后变为可逆 - 氧化电荷量是还原脱附电荷量的1/3,证实了三点吸附模式 4. 表面覆盖度约为反式联噻吩构象理论值的50%,这表明由于存在能量较高的顺式构象,每个分子占据的表面积增加。 5. 氧化波的线型表明相邻分子之间存在静电排斥作用。 这些发现对理解这类分子在金表面上的组装行为和电化学性质具有重要意义。
• Electron-Transfer Properties of Phenyleneethynylene Linkers Bound to Gold via a Self-Assembled Monolayer of Molecular Tripod
  作者：Toshikazu Kitagawa、Takashi Kawano、Takahiro Hase、Ikuma Hayakawa、Katsuyuki Hirai、Takao Okazaki

  DOI：10.3390/molecules23112893

  日期：——

  formation of robust self-assembled monolayers (SAMs) on solid surfaces, where the component molecules are fixed in a strictly upright orientation. In the present study, SAMs of a rigid molecular tripod consisting of an adamantane core and three CH2SH groups were employed to arrange ferrocene on a gold surface through oligo(p-phenyleneethynylene) linkers. Cyclic voltammetry of the monolayers demonstrated high

  三脚架形分子的三点吸附能够在固体表面上形成坚固的自组装单分子层 (SAM)，其中组分分子以严格的直立方向固定。在本研究中，由金刚烷核心和三个 CH2SH 基团组成的刚性分子三脚架的 SAM 被用于通过低聚（对亚苯基乙炔基）接头在金表面上排列二茂铁。单层的循环伏安法表明二茂铁的高表面覆盖率，但相邻二茂铁单元之间的分子相互作用可以忽略不计。这是因为笨重的三脚架框架导致分子间距离延长。通过电化学测量确定了电子从二茂铁通过不同接头长度转移到金表面的速率，
• Metal‐ion sensor composed of self‐assembled monolayer of amine ligand formed by the use of molecular tripod
  作者：Toshikazu Kitagawa、Narimi Hanai、Takashi Kawano、Ayaka Tono、Hiroki Tabata、Tae Kobayashi、Katsuyuki Hirai、Takao Okazaki

  DOI：10.1002/poc.4493

  日期：——

  adsorption-type analysis of the ion binding equilibrium suggested that as much as 70% of the imidazopyridine ligand was actually functioning as a Pb2+ ionophore on the SAM, whereas the rest of the ligand was uncomplexed because of the crowding of the molecules in the SAM. Control experiments using an analogous triad of monothiol revealed a strong advantage in using trithiol; thus, tripod-shaped anchor

  使用由二茂铁、离子载体和具有金刚烷核心的三足三硫醇。SAM 修饰的 Au 电极的伏安法显示，通过添加 Pb 2+ ，二茂铁氧化电位发生较大的正变化 (280 mV) ，检测限为 10 –6  M。 离子的 Langmuir 吸附型分析结合平衡表明多达 70% 的咪唑并吡啶配体实际上起到了 Pb 2+的作用SAM 上的离子载体，而其余配体由于 SAM 中分子的拥挤而未复合。使用类似的单硫醇三元组的对照实验表明使用三硫醇具有很强的优势；因此，三脚架状锚是离子载体作为传感器发挥良好功能所必需的。