1,4,13,16-tetrakis(1-methylethoxy)-8,9,20,21-tetrakis[(4-propyloxy-4-oxo-1-butyl)thio]-25H,27H-dibenzo[b,l]porphyrazine | 325787-38-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1,4,13,16-tetrakis(1-methylethoxy)-8,9,20,21-tetrakis[(4-propyloxy-4-oxo-1-butyl)thio]-25H,27H-dibenzo[b,l]porphyrazine
• 英文别名: Propyl 4-[[5,18,19-tris[(4-oxo-4-propoxybutyl)sulfanyl]-10,13,24,27-tetra(propan-2-yloxy)-2,7,16,21,29,30,31,32-octazaheptacyclo[20.6.1.13,6.18,15.117,20.09,14.023,28]dotriaconta-1(28),2,4,6(32),7,9,11,13,15,17(30),18,20,22,24,26-pentadecaen-4-yl]sulfanyl]butanoate；propyl 4-[[5,18,19-tris[(4-oxo-4-propoxybutyl)sulfanyl]-10,13,24,27-tetra(propan-2-yloxy)-2,7,16,21,29,30,31,32-octazaheptacyclo[20.6.1.13,6.18,15.117,20.09,14.023,28]dotriaconta-1(28),2,4,6(32),7,9,11,13,15,17(30),18,20,22,24,26-pentadecaen-4-yl]sulfanyl]butanoate
• CAS: 325787-38-0
• 化学式: C₆₄H₈₆N₈O₁₂S₄
• 分子量: 1287.7
• InChiKey: ADJLHBLPJRDGIO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.7
• 重原子数：
  88
• 可旋转键数：
  40
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  352
• 氢给体数：
  2
• 氢受体数：
  22

反应信息

• 作为反应物：
  描述：

  1,4,13,16-tetrakis(1-methylethoxy)-8,9,20,21-tetrakis[(4-propyloxy-4-oxo-1-butyl)thio]-25H,27H-dibenzo[b,l]porphyrazine 在 lithium hydroxide 作用下， 以 四氢呋喃 为溶剂， 生成 1,4,13,16-tetrakis(1-methylethoxy)-8,9,20,21-tetrakis[(4-hydroxy-4-oxo-1-butyl)thio]-25H,27H-dibenzo[b,l]porphyrazine
  参考文献：
  名称：

  Surface-Bound Porphyrazines:  Controlling Reduction Potentials of Self-Assembled Monolayers through Molecular Proximity/Orientation to a Metal Surface

  摘要：

  We report the preparation of two novel H-2[pz(A(n);B4-n)] porphyrazines (pzs) which were designed to position themselves quite differently when attached to a surface: one to form a standard self-assembled monolayer (SAM) roughly perpendicular to a surface, the other to lie horizontally along a surface. As the former, we synthesized a pz, 1, where one pyrrole group is functionalized with two thioethers terminated in mercaptides (SR, R = (CH2)(3)CONH(CH2)(2)S-), each protected as a disulfide, and -S-Me is attached to the other pyrrole sites; the latter is a pz, 2, with dialkoxybenzo groups fused to two trans-pyrroles of the pz ring, and SR groups are attached to the other pair of pyrroles. Nanostructures of 1 and 2 were successfully patterned on gold surfaces via dip-pen nanolithography, and the predicted molecular orientation of the resulting structures was confirmed by topographic AFM images. The two pzs exhibit similar reduction potentials in solution. Both show large shifts in potential upon surface binding, with the magnitude of the shift depending on the proximity/orientation of the pz to the surface. The first reduction potential of the "vertically" aligned 1 shifts by ca. +430 mV when incorporated in a binary pz/hexanethiol SAM, while that for 2, which lies flat, shifts by ca. +800 mV; the potential thus shifts by ca. +370 mV upon taking a given pz that stands atop a two-legged insulating "standoff" in a traditional SAM and "laying it down". We suggest these observed effects can be explained by image-charge energetics, and this is supported by a simple model.

  DOI：

  10.1021/ja045270m
• 作为产物：
  描述：

  magnesium n-propoxide 、 1-imino-4,7-bis(1-methylethoxy)-1H-isoindolin-3-amine 、 dimethyl 6,7-dicyano-5,8-dithia-6(Z)-dodecenedioate 在 三氟乙酸 作用下， 以 异丙醇 为溶剂， 生成 1,4,13,16-tetrakis(1-methylethoxy)-8,9,20,21-tetrakis[(4-propyloxy-4-oxo-1-butyl)thio]-25H,27H-dibenzo[b,l]porphyrazine
  参考文献：
  名称：

  Surface-Bound Porphyrazines:  Controlling Reduction Potentials of Self-Assembled Monolayers through Molecular Proximity/Orientation to a Metal Surface

  摘要：

  We report the preparation of two novel H-2[pz(A(n);B4-n)] porphyrazines (pzs) which were designed to position themselves quite differently when attached to a surface: one to form a standard self-assembled monolayer (SAM) roughly perpendicular to a surface, the other to lie horizontally along a surface. As the former, we synthesized a pz, 1, where one pyrrole group is functionalized with two thioethers terminated in mercaptides (SR, R = (CH2)(3)CONH(CH2)(2)S-), each protected as a disulfide, and -S-Me is attached to the other pyrrole sites; the latter is a pz, 2, with dialkoxybenzo groups fused to two trans-pyrroles of the pz ring, and SR groups are attached to the other pair of pyrroles. Nanostructures of 1 and 2 were successfully patterned on gold surfaces via dip-pen nanolithography, and the predicted molecular orientation of the resulting structures was confirmed by topographic AFM images. The two pzs exhibit similar reduction potentials in solution. Both show large shifts in potential upon surface binding, with the magnitude of the shift depending on the proximity/orientation of the pz to the surface. The first reduction potential of the "vertically" aligned 1 shifts by ca. +430 mV when incorporated in a binary pz/hexanethiol SAM, while that for 2, which lies flat, shifts by ca. +800 mV; the potential thus shifts by ca. +370 mV upon taking a given pz that stands atop a two-legged insulating "standoff" in a traditional SAM and "laying it down". We suggest these observed effects can be explained by image-charge energetics, and this is supported by a simple model.

  DOI：

  10.1021/ja045270m

文献信息

• Synthesis of Near-IR Absorbing/Emitting Porphyrazine Derivatives with Tunable Solubility
  作者：Sangwan Lee、Andrew J. P. White、David J. Williams、Anthony G. M. Barrett、Brian M. Hoffman

  DOI：10.1021/jo001220y

  日期：2001.1.1

  We report the synthesis of porphyrazines (pzs), or tetraazaporphyrins, of the form H(2)[pz(A(n;)B(4-n))], where A is [S(CH(2))(3)COOR](2) (R = n-Pr, H) and B is a fused beta,beta'-diisopropyloxybenzo group, including the compounds with n = 4 (6), n = 3 (7) and the trans compound with n = 2 (8) (Scheme 1). The synthesis employs Linstead crossover macrocyclization of dimethyl 6,7-dicyano-5,8-dithia-6(Z)dodecenedioate, MNT(C(4)O(2)Me)2 (2), with 1-imino-4,7-bis(1-methylethoxy)-1H-isoindole-3-amine (4). These pigments were characterized by (1)H NMR, 13C NMR, absorbance/fluorescence spectroscopy, mass spectrometry, and microanalysis. An X-ray crystal structure of 8 is presented. Of particular note, 6-8 display intense near-IR absorbance and dual UV-visible/near-IR emission which are very important in potential biomedical applications, both for cancer therapy (photodyanamic therapy, PDT) and cancer diagnosis (optical tumor imaging). For example, the trans-porphyrazine 8 has an intense long-wavelength absorption at ca. 800 nm (log epsilon = 4.18) and S1 fluorescence at similar to 820 nm, where mammalian tissue is effectively penetrated by light. Transformation of the ester group permits a wide range of functionality and solubility to be generated without change in optical properties. As an example, hydrolysis of these compounds by LiOH in THF/H(2)O gives the corresponding carboxylato-functionalized pigments 9-11, which are described. The last of these dissolves without aggregation in fetal calf serum.
• Varying the Electrochemical Potential and Thickness of Porphyrazine SAMs by Molecular Design
  作者：Hong Zong、Peng Sun、Chad A. Mirkin、Anthony G. M. Barrett、Brian M. Hoffman

  DOI：10.1021/jp905762p

  日期：2009.11.12

  A series of multithiol-functionalized free-base and Zn-coordinated porphyrazines (pz's) have been prepared and characterized as self-assembled monolayers (SAMs) on Au. The synthetic flexibility of the pz's provides a unique opportunity to tune their electronic and chemical characteristics and to control the distance of the redox-active pz macrocycle from the Au surface. This allows us to study the reduction potentials of these surface-bound pz's as a function of film thickness and molecular charge distribution using angle-resolved X-ray photoelectron spectroscopy and cyclic voltammetry. Upon SAM formation, the reduction potentials of all pz's show a significant positive shift from their formal potentials when free in solution (up to similar to +1 V), with the magnitude of the shift inversely related to the Au-pz distance as determined from the film thickness of the pz SAM (thicknesses ranging from 3.5 to 11.8 angstrom). When the pz lies down oil the surface, in a SAM of thickness -3.5 angstrom, the charge distribution within a pz macrocycle also plays a role in determining the potential shift. These observations are consistent with our originally proposed mechanism for potential shifts upon binding to a metal surface based on image charge effects and with the analysis of Liu and Newton (J. Phys. Chem. 1994, 98, 7162).
• Surface-Bound Porphyrazines:  Controlling Reduction Potentials of Self-Assembled Monolayers through Molecular Proximity/Orientation to a Metal Surface
  作者：Benjamin J. Vesper、Khalid Salaita、Hong Zong、Chad A. Mirkin、Anthony G. M. Barrett、Brian M. Hoffman

  DOI：10.1021/ja045270m

  日期：2004.12.1

  We report the preparation of two novel H-2[pz(A(n);B4-n)] porphyrazines (pzs) which were designed to position themselves quite differently when attached to a surface: one to form a standard self-assembled monolayer (SAM) roughly perpendicular to a surface, the other to lie horizontally along a surface. As the former, we synthesized a pz, 1, where one pyrrole group is functionalized with two thioethers terminated in mercaptides (SR, R = (CH2)(3)CONH(CH2)(2)S-), each protected as a disulfide, and -S-Me is attached to the other pyrrole sites; the latter is a pz, 2, with dialkoxybenzo groups fused to two trans-pyrroles of the pz ring, and SR groups are attached to the other pair of pyrroles. Nanostructures of 1 and 2 were successfully patterned on gold surfaces via dip-pen nanolithography, and the predicted molecular orientation of the resulting structures was confirmed by topographic AFM images. The two pzs exhibit similar reduction potentials in solution. Both show large shifts in potential upon surface binding, with the magnitude of the shift depending on the proximity/orientation of the pz to the surface. The first reduction potential of the "vertically" aligned 1 shifts by ca. +430 mV when incorporated in a binary pz/hexanethiol SAM, while that for 2, which lies flat, shifts by ca. +800 mV; the potential thus shifts by ca. +370 mV upon taking a given pz that stands atop a two-legged insulating "standoff" in a traditional SAM and "laying it down". We suggest these observed effects can be explained by image-charge energetics, and this is supported by a simple model.