4-formyl-2,5-dioctyloxyphenylacetylene | 585567-31-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-formyl-2,5-dioctyloxyphenylacetylene
• 英文别名: 1-ethynyl-4-formyl-2,5-dioctyloxybenzene；4-Ethynyl-2,5-bis(octyloxy)benzaldehyde；4-ethynyl-2,5-dioctoxybenzaldehyde
• CAS: 585567-31-3
• 化学式: C₂₅H₃₈O₃
• 分子量: 386.575
• InChiKey: DLBYHRLUSVOIJW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  28
• 可旋转键数：
  18
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-formyl-2,5-dioctyloxyphenylacetylene 在 bis-triphenylphosphine-palladium(II) chloride 哌啶 、 copper(l) iodide 、 碘 作用下， 反应 4.0h， 以78.3%的产率得到1,4-bis(4-formyl-2,5-dioctyloxyphenyl)butadiyne-1,3
  参考文献：
  名称：

  Diyne-Containing PPVs:  Solid-State Properties and Comparison of Their Photophysical and Electrochemical Properties with Those of Their Yne-Containing Counterparts

  摘要：

  Diyne-containing poly(p-phenylene-vinylene)s, 4a-d, of general chemical structure-(Ph-C C-C C-Ph-CH CH-Ph-CH CH-)(n), obtained through polycondensation reactions of 1,4-bis(4-formyl-2,5-dioctyloxyphenyl)-buta-1,3-diyne (2) with various 2,5-dialkoxy-p-xylylenebis(diethylphosphonates), 3a-d, are the subject of this report. The polymers exhibit great disparity in their degree of polymerization, n, which might be ascribed to side-chain-related differences in reactivity of the reactive species during the polycondensation process and which led to n-dependent absorption (solution and solid state) and emission (solution) behaviors of the polymers. Polarizing optical microscopy and differential scanning calorimetry are employed to probe their thermal behavior. The structure is investigated by means of wide-angle X-ray diffraction for both isotropic and macroscopically oriented samples. Comparison of photophysical (experimental and theoretical) and electrochemical properties of the polymers with those of their yne-containing counterparts 6a-d [-(Ph-C C-Ph-CH CH-Ph-CH CH-)(n)] has been carried out. Similar photophysical behavior was observed for both types of polymers despite the difference in backbone conjugation pattern. The introduction of a second yne unit in 4 lowers the HOMO and LUMO levels, thereby enhancing the electron affinity of polymers 4 compared to polymers 6. The "wider opening" introduced by the second yne unit facilitates moreover the movement of charges during the electrochemical processes leading to minimal discrepancy, Delta E-g between the optical and electrochemical band gap energies. Polymers 6, in contrast, show significant side-chain-dependent Delta E-g values. Low turn-on voltages between 2 and 3 V and maximal luminous efficiencies between 0.32 and 1.25 cd/A were obtained from LED devices of configuration ITO/PEDOT:PSS/polymer 4/Ca/Al.

  DOI：

  10.1021/ma0507490
• 作为产物：
  描述：

  溴羟基喹啉 在 四(三苯基膦)钯 potassium fluoride 、 氢氧化钾 、 copper(l) iodide 、 硫酸 、 溶剂黄146 、 二异丙胺 、 pyridinium chlorochromate 、 sodium bromide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 二甲基亚砜 、 甲苯 为溶剂， 反应 50.5h， 生成 4-formyl-2,5-dioctyloxyphenylacetylene
  参考文献：
  名称：

  Supramolecular Ordering, Thermal Behavior, and Photophysical, Electrochemical, and Electroluminescent Properties of Alkoxy-Substituted Yne-Containing Poly(phenylene−vinylene)s

  摘要：

  Alkoxy-substituted and defect-free yne-containing poly(phenylene-vinylene)s, 15a-d, having the general constitutional unit (-Ph-CdropC-Ph-CH=CH-Ph-CH=CH-) synthesized through the olefination reactions of the fluorophoric dialdehyde 7 [1,2-bis(4-formyl-2,5-dialkoxyphenyl)acetylene] with various 2,5-dialkoxy-p-xylylenebis(diethylphosphonates), 14a-d, are reported. A new synthetic route to 1-bromo-2,5-dialkoxybenzaldehyde (starting material for the synthesis of 7) allowing the grafting of all types of alkoxy side chains is also reported. Bulk state properties of the four polymeric materials have been analyzed using various experimental methods giving information on the thermal behavior as well as self-assembling morphologies at different size scales. Crystalline superstructures of either spherulitic or rodlike morphology, comprised of polymeric backbone layers separated by the side chains are identified to develop by nucleation and growth process for symmetrically alkoxy substituted 15a-c. Discrepancy between optical (E-g(opt)) and electrochemical (E-g(ee)) band gaps was observed to be dependent on the bulkiness (15c) and length (15b) of the grafted side chains. Octadecyloxy side chains in 15b not only lead to well structured photoluminescence and electroluminescence spectra and higher fluorescence quantum yields but also allow the design of LED-devices of the configuration ITO/PEDOT/polymer/Ca with improved parameters (eta(ext) = 2.15%, luminance = 5760 cd/m(2)) relative to the octyloxy-substituted polymer 15a (eta(ext) = 0.79%, luminance = 1406 cd/m(2)). Despite the differences in the conjugation pattern between polymers 15 and polymers 17 [(-Ph-CdropC-Ph-CdropC-Ph-CH=CH-Ph-CH=CH-)], an identical chromophore system of structure Ph-CdropC-Ph-CH=CH-Ph-CH=CH-Ph-CdropC-Ph was found to be responsible for their emissive behavior as confirmed by fluorescence kinetics measurements (tau, k(f), k(nr)) and quantum chemical calculations. The differences observed in their solid-state photophysical properties are ascribed to the combined effects of the backbone rigidity (as a function of the number of -CdropC- moieties in the repeating unit) and the nature of the side chains. Moreover less -CdropC- units within polymers 15 lead to the more than 100-fold improvement of their electroluminescent parameters compared to polymers 17.

  DOI：

  10.1021/ma0488111

文献信息

• Dyads and Triads Based on Phenothiazine, Bis(terpyridine)ruthenium(II) Complexes, and Fullerene
  作者：Kevin Barthelmes、Andreas Winter、Ulrich S. Schubert

  DOI：10.1002/ejic.201600793

  日期：2016.11

  donor–photosensitizer–bridge–acceptor (D–P–B–A) triads and D–P dyads for the formation of photoinduced charge-separated species. The structures are based on a phenothiazine unit (D), a bis(terpyridine) [bis(tpy)] ruthenium(II) complex (P), several phenylene(ethynylene)-type spacer units (B), and a pyrrolidino[60]fullerene entity (A). The donor–acceptor distance is between 18 and 37 A and was varied by four different

  我们报告了供体-光敏剂-桥-受体（D-P-B-A）三元组和 D-P 二元组的模块化合成，用于形成光诱导的电荷分离物种。该结构基于吩噻嗪单元 (D)、双(三联吡啶) [双 (tpy)] 钌 (II) 配合物 (P)、几个亚苯基(乙炔) 型间隔单元 (B) 和一个吡咯烷 [60 ]富勒烯实体(A)。供体-受体距离在 18 到 37 A 之间，并由四个不同的桥接单元改变。光物理和电化学表征揭示了地面中的活性部分与激发态之间的某些相互作用。特别是，三元组中减少的基于钌的发射表明发生了由富勒烯实体介导的猝灭过程。
• Investigation of the Photophysical and Electrochemical Properties of Alkoxy-Substituted Arylene−Ethynylene/Arylene−Vinylene Hybrid Polymers
  作者：Daniel Ayuk Mbi Egbe、Bader Cornelia、Jürgen Nowotny、Wolfgang Günther、Elisabeth Klemm

  DOI：10.1021/ma0301395

  日期：2003.7.1

  High-molecular-weight, soluble and thermostable alkoxy-substituted arylene-ethynylene/ arylene-vinylene conjugated polymers, 13 and 14, have been successfully synthesized through the Horner-Wadsworth-Emmons olefination of luminophoric dialdehydes 7 and 9 and bisphosphonate 12 in very good yields. They were characterized through H-1 NMR, C-13 NMR, IR, and elemental analysis. The investigation of their photophysical and electrochemical properties has been carried out. Although almost identical absorption and emission spectra were obtained in dilute chloroform solution for all polymers 13, the full width at half-maximum (fwhm) value of the emission curves depends on the length of the attached side chains. The presence of anthracenylene units in 14 leads to a red shift of its absorption and emission spectra relative to 13. Strong self-reabsorption after excitation in solution was observed for this polymer. The solid-state photophysical properties of 13 and 14 (photoconductivity, absorption and emission spectra, fluorescence quantum yield, Stokes shift, and fwhm) greatly depend on the nature (linear or branched), length, and location of the grafted alkoxy side groups. Photoconductivity is easily detected in polymers having octadecyloxy chains (13aa, 13ab, 14). Long linear (octadecyl, i.e., 13aa) or short branched (2-ethylhexyl, i.e., 13cc) side chains at position R-2 (phenylene-vinylene segment) are necessary to obtain sharp and well-resolved emission spectra accompanied by high fluorescence quantum yields. The quasi-donor (phenylene-vinylene segment)-acceptor (arylene-ethynylene segment) nature of these polymers could explain the great discrepancy between the electrochemical band gap energy, E-g(ec) approximate to 1.60 eV, as obtained from the onset values of the redox potentials in cyclic voltammetry and in differential pulse polarography measurements, and the optical band gap energy, E-g(opt) approximate to 2.30 eV, from the absorption spectra.
• Rhodium-Coordinated Poly(arylene-ethynylene)-<i>alt</i>-Poly(arylene-vinylene) Copolymer Acting as Photocatalyst for Visible-Light-Powered NAD⁺/NADH Reduction
  作者：Kerstin T. Oppelt、Jacek Gasiorowski、Daniel Ayuk Mbi Egbe、Jan Philipp Kollender、Markus Himmelsbach、Achim Walter Hassel、Niyazi Serdar Sariciftci、Günther Knör

  DOI：10.1021/ja506060u

  日期：2014.9.10

  A 2,2'-bipyridyl-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) polymer, acting as a light-harvesting ligand system, was synthesized and coupled to an organometallic rhodium complex designed for photocatalytic NAD(+)/NADH reduction. The material, which absorbs over a wide spectral range, was characterized by using various analytical techniques, confirming its chemical structure and properties. The dielectric function of the material was determined from spectroscopic ellipsometry measurements. Photocatalytic reduction of nucleotide redox cofactors under visible light irradiation (390-650 nm) was performed and is discussed in detail. The new metal-containing polymer can be used to cover large surface areas (e.g. glass beads) and, due to this immobilization step, can be easily separated from the reaction solution after photolysis. Because of its high stability, the polymer-based catalyst system can be repeatedly used under different reaction conditions for (photo)chemical reduction of NAD(+). With this concept, enzymatic, photo-biocatalytic systems for solar energy conversion can be facilitated, and the precious metal catalyst can be recycled.
• Supramolecular Ordering, Thermal Behavior, and Photophysical, Electrochemical, and Electroluminescent Properties of Alkoxy-Substituted Yne-Containing Poly(phenylene−vinylene)s
  作者：Daniel Ayuk Mbi Egbe、Benjamin Carbonnier、Liming Ding、David Mühlbacher、Eckhard Birckner、Tadeusz Pakula、Frank E. Karasz、Ulrich-Walter Grummt

  DOI：10.1021/ma0488111

  日期：2004.10.1

  Alkoxy-substituted and defect-free yne-containing poly(phenylene-vinylene)s, 15a-d, having the general constitutional unit (-Ph-CdropC-Ph-CH=CH-Ph-CH=CH-) synthesized through the olefination reactions of the fluorophoric dialdehyde 7 [1,2-bis(4-formyl-2,5-dialkoxyphenyl)acetylene] with various 2,5-dialkoxy-p-xylylenebis(diethylphosphonates), 14a-d, are reported. A new synthetic route to 1-bromo-2,5-dialkoxybenzaldehyde (starting material for the synthesis of 7) allowing the grafting of all types of alkoxy side chains is also reported. Bulk state properties of the four polymeric materials have been analyzed using various experimental methods giving information on the thermal behavior as well as self-assembling morphologies at different size scales. Crystalline superstructures of either spherulitic or rodlike morphology, comprised of polymeric backbone layers separated by the side chains are identified to develop by nucleation and growth process for symmetrically alkoxy substituted 15a-c. Discrepancy between optical (E-g(opt)) and electrochemical (E-g(ee)) band gaps was observed to be dependent on the bulkiness (15c) and length (15b) of the grafted side chains. Octadecyloxy side chains in 15b not only lead to well structured photoluminescence and electroluminescence spectra and higher fluorescence quantum yields but also allow the design of LED-devices of the configuration ITO/PEDOT/polymer/Ca with improved parameters (eta(ext) = 2.15%, luminance = 5760 cd/m(2)) relative to the octyloxy-substituted polymer 15a (eta(ext) = 0.79%, luminance = 1406 cd/m(2)). Despite the differences in the conjugation pattern between polymers 15 and polymers 17 [(-Ph-CdropC-Ph-CdropC-Ph-CH=CH-Ph-CH=CH-)], an identical chromophore system of structure Ph-CdropC-Ph-CH=CH-Ph-CH=CH-Ph-CdropC-Ph was found to be responsible for their emissive behavior as confirmed by fluorescence kinetics measurements (tau, k(f), k(nr)) and quantum chemical calculations. The differences observed in their solid-state photophysical properties are ascribed to the combined effects of the backbone rigidity (as a function of the number of -CdropC- moieties in the repeating unit) and the nature of the side chains. Moreover less -CdropC- units within polymers 15 lead to the more than 100-fold improvement of their electroluminescent parameters compared to polymers 17.
• Diyne-Containing PPVs:  Solid-State Properties and Comparison of Their Photophysical and Electrochemical Properties with Those of Their Yne-Containing Counterparts
  作者：Daniel Ayuk Mbi Egbe、Benjamin Carbonnier、Elisabeth Lekha Paul、David Mühlbacher、Thomas Kietzke、Eckhard Birckner、Dieter Neher、Ulrich-Walter Grummt、Tadeusz Pakula

  DOI：10.1021/ma0507490

  日期：2005.7.26

  Diyne-containing poly(p-phenylene-vinylene)s, 4a-d, of general chemical structure-(Ph-C C-C C-Ph-CH CH-Ph-CH CH-)(n), obtained through polycondensation reactions of 1,4-bis(4-formyl-2,5-dioctyloxyphenyl)-buta-1,3-diyne (2) with various 2,5-dialkoxy-p-xylylenebis(diethylphosphonates), 3a-d, are the subject of this report. The polymers exhibit great disparity in their degree of polymerization, n, which might be ascribed to side-chain-related differences in reactivity of the reactive species during the polycondensation process and which led to n-dependent absorption (solution and solid state) and emission (solution) behaviors of the polymers. Polarizing optical microscopy and differential scanning calorimetry are employed to probe their thermal behavior. The structure is investigated by means of wide-angle X-ray diffraction for both isotropic and macroscopically oriented samples. Comparison of photophysical (experimental and theoretical) and electrochemical properties of the polymers with those of their yne-containing counterparts 6a-d [-(Ph-C C-Ph-CH CH-Ph-CH CH-)(n)] has been carried out. Similar photophysical behavior was observed for both types of polymers despite the difference in backbone conjugation pattern. The introduction of a second yne unit in 4 lowers the HOMO and LUMO levels, thereby enhancing the electron affinity of polymers 4 compared to polymers 6. The "wider opening" introduced by the second yne unit facilitates moreover the movement of charges during the electrochemical processes leading to minimal discrepancy, Delta E-g between the optical and electrochemical band gap energies. Polymers 6, in contrast, show significant side-chain-dependent Delta E-g values. Low turn-on voltages between 2 and 3 V and maximal luminous efficiencies between 0.32 and 1.25 cd/A were obtained from LED devices of configuration ITO/PEDOT:PSS/polymer 4/Ca/Al.