5-oxa-2,8-dithia[9](2,9)-1,10-phenanthrolinophane | 350014-32-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 5-oxa-2,8-dithia[9](2,9)-1,10-phenanthrolinophane
• 英文别名: 6-Oxa-3,9-dithia-20,23-diazatetracyclo[9.8.4.014,22.017,21]tricosa-1(20),11(23),12,14(22),15,17(21),18-heptaene；6-oxa-3,9-dithia-20,23-diazatetracyclo[9.8.4.014,22.017,21]tricosa-1(20),11(23),12,14(22),15,17(21),18-heptaene
• CAS: 350014-32-3
• 化学式: C₁₈H₁₈N₂OS₂
• 分子量: 342.486
• InChiKey: DCFJOQUEEBNMBT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  85.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  五羰基氯铼(I) 、 5-oxa-2,8-dithia[9](2,9)-1,10-phenanthrolinophane 以 甲苯 为溶剂， 反应 1.0h， 以98%的产率得到C₂₁H₁₈ClN₂O₄ReS₂
  参考文献：
  名称：

  用含1,10-菲咯啉亚基的硫醚冠官能化的 Re（i）衍生物，作为一类新的化学传感器†

  摘要：

  已经合成了一系列发光的fac- [Re（CO）3（L）（NN）] +配合物，其中L是吡啶或咪唑，NN是混合的供体五齿硫醚冠的1,10-菲咯啉亚基，并且已经分析了它们的发光特性。然后，杂金属Re（I）/ Au（I）配合物，其中Au（I）片段直接键合到咪唑配体上；杂金属Re（I）/ Ag（I）配合物，其中银片段配位S-供体环的硫醚连接基也已制备。对它们的发光特性的分析表明，Re（I）/ Ag（I）衍生物，在银中心与大环单元脂族链的S-供体原子配位时。

  DOI：

  10.1039/c5dt02723c
• 作为产物：
  描述：

  1,10-菲啰啉-2,9-二甲醛 在 sodium tetrahydroborate 、 氯化亚砜 、 caesium carbonate 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 生成 5-oxa-2,8-dithia[9](2,9)-1,10-phenanthrolinophane
  参考文献：
  名称：

  用含1,10-菲咯啉亚基的硫醚冠官能化的 Re（i）衍生物，作为一类新的化学传感器†

  摘要：

  已经合成了一系列发光的fac- [Re（CO）3（L）（NN）] +配合物，其中L是吡啶或咪唑，NN是混合的供体五齿硫醚冠的1,10-菲咯啉亚基，并且已经分析了它们的发光特性。然后，杂金属Re（I）/ Au（I）配合物，其中Au（I）片段直接键合到咪唑配体上；杂金属Re（I）/ Ag（I）配合物，其中银片段配位S-供体环的硫醚连接基也已制备。对它们的发光特性的分析表明，Re（I）/ Ag（I）衍生物，在银中心与大环单元脂族链的S-供体原子配位时。

  DOI：

  10.1039/c5dt02723c

文献信息

• Conformationally locked pentadentate macrocycles containing the 1,10-phenanthroline unit. Synthesis and crystal structure of 5-oxa-2,8-dithia[9](2,9)-1,10-phenanthrolinophane (L) and its coordination properties to NiII, PdII, PtII, RhIII and RuII †
  作者：Massimiliano Arca、Alexander J. Blake、Jaume Casabò、Francesco Demartin、Francesco A. Devillanova、Alessandra Garau、Francesco Isaia、Vito Lippolis、Raikko Kivekas、Vicent Muns、Martin Schröder、Gaetano Verani

  DOI：10.1039/b100493j

  日期：——

  The complexation of the new mixed thia–aza–oxa macrocycle 5-oxa-2,8-dithia[9](2,9)-1,10-phenanthrolinophane (L) containing the 1,10-phenanthroline unit with NiII, PdII, PtII, RhIII and RuII has been investigated. The results have been compared with those obtained with the structurally related ligand 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane (L′). The most stable conformations of both ligands have been calculated in order to understand their change upon metal complexation and for L good agreement has been found with the conformations observed in the crystal structure of L·½H2O. The single-crystal structures of [Ni(L)Cl]BF4 and [Ru(L)(PPh3)][PF6]2·1//4MeCN reveal a N2S2O coordination sphere about NiII and RuII, with the macrocyclic ligand in a folded conformation and with the sixth coordination site taken up by Cl− or PPh3, respectively. For [Pd(L)][BF4]2 an [N2S2 + O] coordination is observed, with the O-donor interacting weakly with the metal centre at the apical position of a square-based coordination sphere. 13C and 1H NMR spectroscopic studies indicate that the complexes are not fluxional in solution, with the ligand imposing the same coordination sphere as observed in the solid state. 13C NMR spectroscopy has also helped in elucidating the stereochemistry of [Rh(L)Cl2]BF4 for which no suitable crystals could be grown: the two Cl− ligands are mutually trans with the N2S2 donor set of the macrocyclic ligand occupying the equatorial positions of an octahedral coordination sphere and with the O-donor atom left un-coordinated. The redox properties of all the complexes in MeCN have been studied.

  含有 1,10-菲咯啉单元的新型混合硫杂-氮杂-氧杂大环 5-oxa-2,8-二硫杂[9](2,9)-1,10-菲咯啉 (L) 与 NiII、PdII 的络合、PtII、RhIII 和 RuII 已被研究。结果与结构相关配体 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane (L') 获得的结果进行了比较。计算了两种配体最稳定的构象，以了解它们在金属络合时的变化，并且发现 L 与 L·½H2O 晶体结构中观察到的构象具有良好的一致性。 [Ni(L)Cl]BF4和[Ru(L)(PPh3)][PF6]2·1//4MeCN的单晶结构揭示了围绕NiII和RuII的N2S2O配位球，其中大环配体处于折叠状态构象和第六配位点分别由 Cl− 或 PPh3 占据。对于 [Pd(L)][BF4]2，观察到 [N2S2 + O] 配位，O 供体与方形配位球顶端位置的金属中心相互作用较弱。 13C 和 1H NMR 光谱研究表明，配合物在溶液中不流动，配体施加与固态中观察到的相同的配位球。 13C NMR 光谱还有助于阐明 [Rh(L)Cl2]BF4 的立体化学，但无法生长合适的晶体：两个 Cl− 配体与占据赤道位置的大环配体的 N2S2 供体组相互反式。八面体配位球且 O 供体原子未配位。研究了 MeCN 中所有配合物的氧化还原性质。
• Complexes of CuII with mixed-donor phenanthroline-containing macrocycles: analysis of their structural, redox and spectral properties in the context of Type-1 blue copper proteins biomimetic models
  作者：Massimiliano Arca、Gholamhassan Azimi、Francesco Demartin、Francesco A. Devillanova、Lluis Escriche、Alessandra Garau、Francesco Isaia、Raikko Kivekas、Vito Lippolis、Vicent Muns、Alessandro Perra、Mojtaba Shamsipur、Luigi Sportelli、Abdollah Yari

  DOI：10.1016/j.ica.2005.01.014

  日期：2005.4

  The macrocycles L-1-L-3 having N2S2O-, N2S2-, and N2S3-donor sets, respectively, and incorporating the 1,10-phenanthroline unit interact in EtOH and MeCN solutions with Cu-II to give 1:1 [M(L)](2+) complex species. The compounds [Cu(L-1)(ClO4)]ClO4 (1), [Cu(L-2)(ClO4)]ClO4 center dot 1/2H(2)O (2) and [Cu(L-3)](ClO4)(2) (3) were isolated at the solid state and the first two also characterised by X-ray diffraction studies. The conformation adopted by L-1 and L 2 in the cation complexes reveals the aliphatic portion of the rings folded over the plane containing the heteroaromatic moiety with the ligands encapsulating the metal centre within their cavity by imposing. respectively, a square-based pyramidal and a square planar geometry. In both complexes, the metal ion completes its coordination sphere by interacting with a ClO4- ligand. The compound [Cu(L-3)(2)](PF6)(2) (4) containing a 1:2 cation complex was also isolated at the solid state: EPR spectroscopy measurements suggest the presence of a CuN4 chromophore in this complex. The EPR and electronic spectral features of 1-4 have been studied and their redox properties examined in comparison with those observed for Type-1 blue copper proteins.The reactivity of L-1-L-3 has also been tested toward stoichiometric amounts of the Cut salt [CuCl(PPh3)(3)], (c) 2005 Elsevier B.V. All rights reserved.
• Fluorometric Chemosensors. Interaction of Toxic Heavy Metal Ions Pb^II, Cd^II, and Hg^II with Novel Mixed-Donor Phenanthroline-Containing Macrocycles:  Spectrofluorometric, Conductometric, and Crystallographic Studies
  作者：M. Carla Aragoni、Massimiliano Arca、Francesco Demartin、Francesco A. Devillanova、Francesco Isaia、Alessandra Garau、Vito Lippolis、Fahimeh Jalali、Ulrich Papke、Mojtaba Shamsipur、Lorenzo Tei、Abdollah Yari、Gaetano Verani

  DOI：10.1021/ic020270d

  日期：2002.12.1

  The macrocycles L-1-L-3 incorporating N2S3-, N2S2O-, and N2S2-donor sets, respectively, and containing the 1,10-phenanthroline unit interact in acetonitrile solution with heavy metal ions such as Pb-II, Cd-II, and Hg-II to give 1:1 ML, 1:2 ML2, and 2:1 M2L complex species, which specifically modulate the photochemical properties of the ligands. The stoichiometry of the complex species formed during spectrofluorometric titrations and their formation constants in MeCN at 25 degreesC were determined from fluorescence vs M-II/L molar ratio data. The complexes [Pb(L-1)][ClO4](2)1/2H(2)O (1), [Pb(L-2)][ClO4](2).MeNO2 (1a), [Pb(L-3)(2)][ClO4](2).2MeCN (1b), and [Cd(L-3)][NO3](2) (2b) were also characterized by X-ray diffraction studies. The conformation adopted by L-1-L-3 in these species reveals the aliphatic portion of the rings folded over the plane containing the heteroaromatic moiety with the ligands trying to encapsulate the metal center within their cavity, In 1, 1a, and 2b the metal ion completes the coordination sphere by interacting with counteranion units and solvent molecules. On the contrary, the 1:2 complex 1b shows Pb-II sandwiched between two symmetry-related molecules of L-3 reaching an overall [4N + 4S] eight-coordination.
• Re(<scp>i</scp>) derivatives functionalised with thioether crowns containing the 1,10-phenanthroline subunit as a new class of chemosensors
  作者：Arianna Casula、Valentina Nairi、Vanesa Fernández-Moreira、Antonio Laguna、Vito Lippolis、Alessandra Garau、M. Concepción Gimeno

  DOI：10.1039/c5dt02723c

  日期：——

  fac-[Re(CO)3(L)(NN)]+ complexes, where L is a pyridine or an imidazole and NN is the 1,10-phenanthroline subunit of mixed donor pentadentate thioether crowns have been synthesised and their luminescence properties have been analysed. Then, heterometallic Re(I)/Au(I) complexes, with the Au(I) fragment bonded directly to the imidazole ligand, and heterometallic Re(I)/Ag(I) complexes, with the silver fragment coordinating

  已经合成了一系列发光的fac- [Re（CO）3（L）（NN）] +配合物，其中L是吡啶或咪唑，NN是混合的供体五齿硫醚冠的1,10-菲咯啉亚基，并且已经分析了它们的发光特性。然后，杂金属Re（I）/ Au（I）配合物，其中Au（I）片段直接键合到咪唑配体上；杂金属Re（I）/ Ag（I）配合物，其中银片段配位S-供体环的硫醚连接基也已制备。对它们的发光特性的分析表明，Re（I）/ Ag（I）衍生物，在银中心与大环单元脂族链的S-供体原子配位时。