[Sb(OMe)Br(tpp)]Br | 154443-60-4

• 英文名称: [Sb(OMe)Br(tpp)]Br
• 英文别名: bromo(methoxo)(tetraphenylporphyrinato)antimony(V) bromide；bromo(methoxo)tetraphenylporphyrinatoantimony(V) bromide；bromo(methoxo)tetraphenylporphyrinatoantimony bromide
• CAS: 154443-60-4
• 化学式: Br*C₄₅H₃₁BrN₄OSb
• 分子量: 925.325
• InChiKey: ZYJJKKKWKUVTFB-GVHKZQBISA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Sb(OMe)Br(tpp)]Br 在 三乙胺 作用下， 生成 tetraphenylporphyrin
  参考文献：
  名称：

  Effects of an Axial Amino Ligand on the Spectroscopic and Electrochemical Properties of Amino(methoxo)(tetraphenylporphyrinato)antimony(V) Complexes

  摘要：

  我们研究了轴向氨基配体对烷基氨基（甲氧基）（四苯基卟啉）锑(V)溴化物1和苯胺（甲氧基）（四苯基卟啉）锑(V)溴化物2的光谱和电化学性质的影响。对1和2的荧光测量显示，它们的荧光量子产率低于二羟基（四苯基卟啉）锑(V)溴化物（3），这是由于轴向氨基配体向激发的卟啉环发生了分子内电子转移（ET）。通过质子化轴向氮原子，添加质子增强了荧光，从而防止了电子转移。通过荧光量子产率（Φf）与质子浓度的滴定曲线，我们估计了1的轴向氨基配体的共轭酸的酸解离常数（pKa）为4.41–5.03。2的还原电位（E1⁄2red）强烈依赖于p位取代基（X）对轴向苯胺基团的电子效应，而甲氧基（p-取代苯氧基）（四苯基卟啉）锑(V)溴化物的E1⁄2red几乎不受苯氧配体上p位取代基的影响。这些观察结果被解释为反映了轴向氨基配体参与了通过PM3方法为2计算的LUMO。

  DOI：

  10.1246/bcsj.81.583
• 作为产物：
  描述：

  anilino(methoxo)(tetraphenylporphyrinato)antimony(V) bromide 在 四乙基溴化铵 、 三氟乙酸 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以22%的产率得到[Sb(OMe)Br(tpp)]Br
  参考文献：
  名称：

  Effects of an Axial Amino Ligand on the Spectroscopic and Electrochemical Properties of Amino(methoxo)(tetraphenylporphyrinato)antimony(V) Complexes

  摘要：

  我们研究了轴向氨基配体对烷基氨基（甲氧基）（四苯基卟啉）锑(V)溴化物1和苯胺（甲氧基）（四苯基卟啉）锑(V)溴化物2的光谱和电化学性质的影响。对1和2的荧光测量显示，它们的荧光量子产率低于二羟基（四苯基卟啉）锑(V)溴化物（3），这是由于轴向氨基配体向激发的卟啉环发生了分子内电子转移（ET）。通过质子化轴向氮原子，添加质子增强了荧光，从而防止了电子转移。通过荧光量子产率（Φf）与质子浓度的滴定曲线，我们估计了1的轴向氨基配体的共轭酸的酸解离常数（pKa）为4.41–5.03。2的还原电位（E1⁄2red）强烈依赖于p位取代基（X）对轴向苯胺基团的电子效应，而甲氧基（p-取代苯氧基）（四苯基卟啉）锑(V)溴化物的E1⁄2red几乎不受苯氧配体上p位取代基的影响。这些观察结果被解释为反映了轴向氨基配体参与了通过PM3方法为2计算的LUMO。

  DOI：

  10.1246/bcsj.81.583
• 作为试剂：
  描述：

  环己烯 在 [Sb(OMe)Br(tpp)]Br 、 水 、 paraquat dichloride 作用下， 以 乙腈 为溶剂， 生成 1,2-环己二醇 、 氧化环己烯 、 2-环己烯醇
  参考文献：
  名称：

  Inoue, Haruo; Okamoto, Takanobu; Kameo, Yohji, Journal of the Chemical Society. Perkin transactions I, 1994, # 1, p. 105 - 112

  摘要：

  DOI：

文献信息

• Water-soluble Porphyrin Easily Derived from Tetraphenylporphyrin: Alkyloxo(methoxo)porphyrinatoantimony Bromides
  作者：Jin Matsumoto、Tsutomu Shiragami、Masahide Yasuda

  DOI：10.1246/cl.2008.886

  日期：2008.8.5

  In order to develop water-soluble porphyrins, alkyloxo(methoxo)porphyrinatoantimony bromides (alkyl = decyl, dodecyl, and octadecyl) were prepared. These complexes have more than 200 mg/100 g of solubility in aqueous solution. From the analysis of absorption spectra and surface tension, it was elucidated that the porphyrin complexes are present as aggregates in aqueous solution.

  为了开发水溶性卟啉，制备了烷氧（甲氧）卟啉钽溴化物（烷基 = 十烷、十二烷和十八烷）。这些络合物在水溶液中的溶解度超过200毫克/100克。通过对吸收光谱和表面张力的分析，阐明了卟啉络合物在水溶液中以聚集体的形式存在。
• Water-solubilization of alkyloxo(methoxo)porphyrinatoantimony bromides
  作者：Jin Matsumoto、Shin-ichiro Tanimura、Tsutomu Shiragami、Masahide Yasuda

  DOI：10.1039/b911227h

  日期：——

  In order to develop water-soluble porphyrins, alkyloxo(methoxo)porphyrinatoantimony bromides (alkyl = hexyl (1a), decyl (1b), dodecyl (1c), tetradecyl (1d), octadecyl (1e)) were prepared. 1 had more than 1 mmol dm−3 of solubility in water. From the dependence of the half-width of the bands in the absorption spectra and surface tension on the concentration of 1, it was estimated that 1b–d were present as aggregates in concentrations higher than 10 μmol dm−3. From the NMR analysis in D2O, it was deduced that the alkyloxo ligands of 1 were arranged alternately in the aggregates. The diameter of the aggregates of 1 in water was determined to be around 100 nm by the dynamic light scattering method. Since the solubilities of di(methoxo)tetraphenylporphyrinatoantimony bromide and 5-(4′-decyloxyphenyl)-10,15,20-triphenylporphyrinato(dimethoxo)antimony(V) bromide were low, it was calculated that the long alkyl axial ligands were requisite for the high solubility in water.

  为了开发水溶性卟啉，制备了烷氧（甲氧）卟啉铋溴化物（烷基 = 六基（1a）、十基（1b）、十二基（1c）、十四基（1d）、十八基（1e））。1在水中的溶解度超过1 mmol dm−3。从吸收光谱中带宽与1浓度的关系以及表面张力来看，可以估计1b-d在浓度高于10 μmol dm−3时以聚集体的形式存在。通过在D2O中的NMR分析，推测1的烷氧配体在聚集体中交替排列。通过动态光散射法测定1在水中的聚集体直径约为100纳米。由于二（甲氧基）四苯基卟啉铋溴化物和5-（4'-十基氧基苯基）-10,15,20-三苯基卟啉（甲氧基）铋（V）溴化物的溶解度较低，因此推算出长烷基轴向配体是水中高溶解度的必要条件。
• Amino(porphyrinato)antimony(V) Complexes as a Fluorosensor for Selective and Sensitive Detection of Trivalent Metal Cations
  作者：Shin-ichiro Tsunami、Hirotaka Fujiwara、Jin Matsumoto、Tsutomu Shiragami、Masahide Yasuda

  DOI：10.1246/bcsj.20090206

  日期：2010.1.15

  effects of metal cations on the fluorescence quantum yield (Φ f ) were investigated for weak-emissive amino(tetraphenylporphyrinato)antimony(V) bromide (1). When the μmol dm -3 of trivalent metal cations such as Al 3+ , Ga 3+ , In 3+ , and Lu 3+ were added to MeCN solution of 1, the Φ f was remarkably enhanced. The dependences of Soret band shift and Φ f upon the addition of trivalent metal cations revealed

  研究了金属阳离子对弱发射氨基（四苯基卟啉）溴化锑 (V) 的荧光量子产率 (Φ f ) 的累加效应 (1)。当Al 3+ 、Ga 3+ 、In 3+ 和Lu 3+ 等三价金属阳离子的μmol dm -3 添加到1的MeCN溶液中时，Φ f 显着提高。Soret 能带位移和 Φ f 对添加三价金属阳离子的依赖性表明，通过将三价金属阳离子配位到 1. 1 的轴向氮原子，可以防止从 S 2 状态到部分电荷转移状态的转变。用于检测 μmol dm -3 三价金属阳离子的选择性荧光传感器。
• Non-aggregated Intercalation of Dicationic Tetraphenylporphyrinatoantimony(V) Complexes into Smectite Clay Layers
  作者：Tsutomu Shiragami、Keiko Nabeshima、Jin Matsumoto、Masahide Yasuda、Haruo Inoue

  DOI：10.1246/cl.2003.484

  日期：2003.6

  Adsorption and intercalation of +2 charged cationic [3-(trimethylammonio)propoxo(methoxo)(tetraphenylporphyrinato)antimony(V)]2+ (1a) into an artificially synthesized smectite clay were studied. The red shift of Soret band in UV-spectra for 1a in an aqueous colloidal clay solution and analyses of X-ray diffraction of the obtained complex between 1a and the clay indicate the intercalation of 1a into the

  研究了+2 带电阳离子[3-(三甲基氨)丙氧(甲氧)(四苯基卟啉)锑(V)]2+ (1a) 吸附和嵌入人工合成的蒙脱石粘土中。胶体粘土水溶液中 1a 的紫外光谱中 Soret 谱带的红移和 1a 与粘土之间所获得复合物的 X 射线衍射分析表明 1a 嵌入到粘土夹层中。轴向配体上的铵阳离子部分导致 1a 有效地非聚集嵌入粘土中。
• Effects of Axial Ligands on the Formation of a Layered Structure in Mono- and Di-Cationic Charged Tetraphenylporphyrinatoantimony(V)/Synthetic Clay Composites
  作者：Tsutomu Shiragami、Keiko Nabeshima、Satoko Nakashima、Jin Matsumoto、Shinsuke Takagi、Haruo Inoue、Masahide Yasuda

  DOI：10.1246/bcsj.78.2251

  日期：2005.12

  Novel metalloporphyrin–clay composites were prepared from a synthetic clay (Sumecton SA: SSA) and cationic tetraphenylporphyrinatoantimony(V) bromide (SbTPP, 1–4) having various axial ligands. Both the crystal structure for SbTPP–SSA composites and the adsorption behaviors of SbTPP into SSA sheets are investigated regarding the relation to the structure of an axial ligand at SbTPP by measuring the X-ray diffraction (XRD), IR, UV–vis, and fluorescence spectroscopy. The XRD analysis revealed that powdered SbTPP–SSA composites could take a layered structure for 1, and an amorphous structure for 2, respectively. The IR spectrum of naked SSA showed a broad absorption band around 3000–3600 cm−1, which can probably be assigned as some adsorbed water molecules onto SSA. The intensity of the broad absorption band became weaker with an increase of the loading level (%LL), which was defined as a ratio of the concentration of the cationic sites of 1–4 to the concentration of anionic sites of SSA. The band completely disappeared at 100%LL in both 2–SSA and 4–SSA composites with the amorphous structure, whereas the band remained even at 100%LL in both 1–SSA and 3–SSA composites with the layered structure. Information about an aggregation state of 1–4 into SSA was obtained by measuring both the UV–vis absorption spectra of 1–4 in an aqueous colloidal clay solution and the fluorescence spectra of SbTPP–SSA composites in the solid state by using a confocal laser scanning fluorescence microscope. Each spectral data indicated that the ammonium cationic part on an axial ligand of 1 only led to effective non-aggregated adsorption onto SSA sheets, while 2–4 were located with the aggregated state on SSA sheets. These results also support that an axial ligand structure can control not only the formation of the crystal structure, but also the adsorption behaviors with aggregation or non-aggregation onto SSA sheets.

  新型金属卟啉-粘土复合材料由合成粘土（Sumecton SA：SSA）和具有各种轴向配体的阳离子四苯基卟啉锑（V）溴化物（SbTPP，1-4）制备而成。通过测量 X 射线衍射 (XRD)、IR、UV-vis 和荧光光谱法。 XRD 分析表明，粉末状 SbTPP-SSA 复合材料可分别采用层状结构（1）和非晶结构（2）。裸露SSA的红外光谱显示出3000-3600 cm−1附近的宽吸收带，这可能可以归因于SSA上吸附的一些水分子。宽吸收带的强度随着负载水平（%LL）的增加而变弱，负载水平被定义为1-4的阳离子位点浓度与SSA阴离子位点浓度的比率。在具有非晶结构的 2-SSA 和 4-SSA 复合材料中，在 100%LL 时，能带完全消失，而在具有层状结构的 1-SSA 和 3-SSA 复合材料中，能带甚至在 100%LL 时仍然存在。通过使用共焦激光测量胶体粘土水溶液中 1-4 的紫外可见吸收光谱和固态 SbTPP-SSA 复合材料的荧光光谱，获得了有关 1-4 聚集成 SSA 的信息。扫描荧光显微镜。每个光谱数据表明，1 的轴向配体上的铵阳离子部分仅导致在 SSA 片上有效的非聚集吸附，而 2-4 则以聚集状态位于 SSA 片上。这些结果还支持轴向配体结构不仅可以控制晶体结构的形成，还可以控制 SSA 片上聚集或非聚集的吸附行为。