[SbBr2(tpp)]Br | 379677-75-5

• 英文名称: [SbBr2(tpp)]Br
• 英文别名: dibromo(5,10,15,20-tetraphenylporphyrinato)antimony(V) bromide；dibromo(tetraphenylporphyrinato)antimony(V) bromide；dibromo[tetraphenylporphyrinato]antimony(V) bromide；dibromotetraphenylporphyrinatoantimony(V) bromide；dibromotetraphenylporphyrinatoantimony bromide
• CAS: 379677-75-5
• 化学式: Br*C₄₄H₂₈Br₂N₄Sb
• 分子量: 974.195
• InChiKey: VYFKBXWOMJDIPW-GVHKZQBISA-K

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：

  [SbBr2(tpp)]Br 在 水 作用下， 以 乙腈 为溶剂， 生成 bromo(hydroxy)(5,10,15,20-tetraphenylporphyrinato)antimony(V) bromide
  参考文献：
  名称：

  氨基（卟啉）锑（V）配合物作为荧光传感器用于三价金属阳离子的选择性和灵敏检测

  摘要：

  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。

  DOI：

  10.1246/bcsj.20090206

文献信息

• Effects of an Axial Amino Ligand on the Spectroscopic and Electrochemical Properties of Amino(methoxo)(tetraphenylporphyrinato)antimony(V) Complexes
  作者：Shin-ichiro Tsunami、Kousuke Tanaka、Jin Matsumoto、Tsutomu Shiragami、Masahide Yasuda

  DOI：10.1246/bcsj.81.583

  日期：2008.5.15

  We investigated the effects of an axial amino ligand on the spectroscopic and electrochemical properties of alkylamino(methoxo)(tetraphenylporphyrinato)antimony(V) bromide 1 and anilino(methoxo)(tetraphenylporphyrinato)antimony(V) bromide 2. Fluorescence measurements of 1 and 2 showed that their fluorescence quantum yields were lower than that of dihydroxo(tetraphenylporphyrinato)antimony(V) bromide (3) due to intramolecular electron transfer (ET) from the axial amino ligand to the excited porphyrin ring. Fluorescence was enhanced by the addition of a proton, which was caused by the protonation of the axial nitrogen atom, thereby preventing ET. From the titration curves of fluorescence quantum yield (Φf) versus proton concentration, we estimated the acid dissociation constants (pKa) for the conjugate acid of the axial amino ligand of 1 to be 4.41–5.03. The reduction potentials (E1⁄2red) of 2 depended strongly on the electronic effect of the p-substituents (X) on the axial aniline group whereas the E1⁄2red of methoxo(p-substituted-phenoxo)(tetraphenylporphyrinato)antimony(V) bromide was little affected by the p-substituents on the phenoxo ligand. These observations were interpreted as reflecting the participation of the axial amino ligand in the LUMO, calculated for 2 by the PM3 method.

  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。
• 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。
• Effects of an Axial Ligand on the Reduction Potential, Proton Dissociation, and Fluorescence Quantum Yield of Hydroxo(porphyrinato)antimony(V) Complexes
  作者：Tsutomu Shiragami、Yoshito Andou、Yuichiro Hamasuna、Futoshi Yamaguchi、Kensuke Shima、Masahide Yasuda

  DOI：10.1246/bcsj.75.1577

  日期：2002.7

  The substituent effects on the reduction potentials (E1/2red), the proton dissociation constants of a hydroxo ligand (Ka), and the fluorescence quantum yields (Φ) in aryloxo(hydroxo)tetraarylporphyrinatoantimony(V) complexes were investigated. The E1/2red and Ka values were affected by substituents in the axial aryloxo ligand but, little affected by substituents in the porphyrin ring. Since E1/2red

  研究了取代基对还原电位 (E1/2red)、羟基配体的质子解离常数 (Ka) 和芳氧基(羟基)四芳基卟啉锑 (V) 配合物中的荧光量子产率 (Φ) 的影响。E1/2red 和 Ka 值受轴向芳氧基配体中取代基的影响，但受卟啉环中取代基的影响很小。由于四芳基卟啉锑(V)配合物的E1/2red高于其他金属卟啉配合物，表明金属轨道对配合物的LUMO能级有很大贡献，这与E1/2red和Ka值有关。因此，轴向芳氧基配体对 E1/2red 和 Ka 值的取代作用归因于锑离子的电子密度，这影响了配合物的 LUMO 能级。此外，卟啉部分的 Φ 取决于轴向芳氧基配体的氧化电位和所用溶剂的极性。荧光...
• 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。
• 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。