5-pentafluorophenyl-1,3,7,9-tetramethyldipyrrin | 1394285-02-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5-pentafluorophenyl-1,3,7,9-tetramethyldipyrrin
• 英文别名: 2-[(3,5-dimethyl-1H-pyrrol-2-yl)-(2,3,4,5,6-pentafluorophenyl)methylidene]-3,5-dimethylpyrrole
• CAS: 1394285-02-9
• 化学式: C₁₉H₁₅F₅N₂
• 分子量: 366.334
• InChiKey: RAQXQPZNTDYHMF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.51
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  28.15
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  5-pentafluorophenyl-1,3,7,9-tetramethyldipyrrin 在 N-溴代丁二酰亚胺(NBS) 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 2,6-dibromo-8-pentafluorophenyl-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  卤代 3,5-二甲基- 和 1,3,5,7-四甲基-内消旋-五氟苯基 BODIPY 染料的光动力抗菌活性

  摘要：

  研究了四种内消旋五氟苯基 BODIPY 染料对金黄色葡萄球菌的光动力抗微生物化学疗法 (PACT) 活性，以确定与在 BODIPY 核心上引入不同取代基相关的结构-性质关系。合成并表征了在 2,6 位（2a和3a ）具有溴和碘原子的 1,3,5,7-四甲基染料以及在 1,2,6 位被四溴化的 3,5-二甲基染料,7-位 ( 2b ) 或二碘化 ( 3b) 在 2,6-位置。相对于二溴和四溴染料，在 BODIPY 核心的 2,6 位加入碘原子增强了 PACT 活性。用质子取代 1,7-位的甲基形成3b导致比3a的情况更高的 PACT 活性，因为在 1,7-位不存在与甲基相关的空间位阻允许中间芳基环旋转更接近的平面π-BODIPY 核心系统。四溴化染料被发现具有最低的 PACT 活性，因为它在溶液中缺乏稳定性并且被研究的细菌吸收不良。选择吸电子的五氟苯基来降低 BODIPY 核心染料的偶极矩，因为在用硫代甲基苯基制备

  DOI：

  10.1142/s1088424622500535
• 作为产物：
  描述：

  5-pentafluorophenyl-1,3,7,9-tetramethyldipyrromethane 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以63%的产率得到5-pentafluorophenyl-1,3,7,9-tetramethyldipyrrin
  参考文献：
  名称：

  二吡啶-铱(III)配合物在光动力治疗和抗菌光动力灭活中的应用

  摘要：

  生物靶向光敏剂的产生对于光动力疗法和抗菌（光）疗法的新兴领域至关重要。提出了一种合成策略，其中使用螯合二吡啉部分来增强铱（III）金属配合物的已知光活性。因此，形成的复合物可以通过一系列靶向基团在其化学活性反应位点以简便的方式进行官能化。具有 N- 和 O- 取代基的二吡啶通过与各自的 Cp*-铱(III) 和 ppy-铱(III) 前体络合得到 (dipy) 铱 (III) 络合物 (dipy=dipyrrinato, Cp*=pentamethyl-η 5 ‐环戊二烯基，ppy=2-苯基吡啶基）。类似地，缺电子的[Ir III (dipy)(ppy) 2 ]配合物可用于后官能化，形成烯基、炔基和糖基铱(III)配合物。这些复合物的光毒性活性已在有光和无光的细胞和细菌测定中进行了评估； [Ir III (Cl)(Cp*)(dipy)]配合物和糖取代的铱(III)配合物作为光医学候选者表现

  DOI：

  10.1002/chem.202004776

文献信息

• Optical limiting properties of D-π-A BODIPY dyes in the presence and absence of methyl groups at the 1,7-positions
  作者：Aviwe May、John Mack、Tebello Nyokong

  DOI：10.1142/s1088424620500315

  日期：2020.9

  The optical limiting properties of three meso-pentafluorophenylstyrylBODIPY dyes are investigated in the presence and absence of methyl groups at the 1,7-positions that hinder free rotation of the meso-aryl group. Pentafluorophenyl groups are introduced at the meso-position, while 4-diethylaminostyryl groups are introduced at the 3- and/or 5-positions to form dyes with strong donor-[Formula: see text]-acceptor (D-[Formula: see text]-A) properties to enhance the dipole moment of the molecule. Favorable optical limiting properties are obtained for all three dyes, with the highest second-order hyperpolarizability value obtained for a monostyryl dye with no methyl groups at the 1,7-position. Bromination at the 2,6-positions of a 1,7-methyl substituted dye is found to result in second-order hyperpolarizability that is an order of magnitude lower than that calculated for the analogous non-halogenated dye.

  在 1,7 位存在和不存在阻碍介芳基自由旋转的甲基的情况下，研究了三种介五氟苯基苯乙烯-BODIPY 染料的光学限制特性。在中位引入了五氟苯基基团，而在 3-和/或 5-位引入了 4-二乙基氨基苯乙烯基团，从而形成了具有强供体-[式：见正文]-受体（D-[式：见正文]-A）特性的染料，增强了分子的偶极矩。这三种染料都具有良好的光学限制特性，其中 1,7 位没有甲基的单苯乙烯基染料的二阶超极化率值最高。研究发现，1,7-甲基取代染料的 2,6-位溴化会导致二阶超极化率，而二阶超极化率要比计算出的类似非卤化染料的二阶超极化率低一个数量级。
• Synthesis and characterisation of neutral mononuclear cuprous complexes based on dipyrrin derivatives and phosphine mixed-ligands
  作者：Xiaohui Liu、Hongmei Nan、Wei Sun、Qikai Zhang、Mingjian Zhan、Luyi Zou、Zhiyuan Xie、Xiao Li、Canzhong Lu、Yanxiang Cheng

  DOI：10.1039/c2dt30618b

  日期：——

  Heteroleptic neutral mononuclear cuprous complexes with dipyrrin derivatives and phosphine mixed-ligands including 1,3,7,9-tetramethyldipyrrin (1), 5-phenyl-1,3,7,9-tetramethyldipyrrin (2), 2,8-dibromo-1,3,7,9-tetramethyldipyrrin (3), 1,9-dichloro-5-phenyldipyrrin (4), 1,9-dibromo-5-phenyldipyrrin (5), 5-pentafluorophenyl-1,3,7,9-tetramethyldipyrrin (6) and 1,5,9-triphenyldipyrrin (7) have been synthesized and fully characterized. The central Cu(I) atoms of these complexes in general formulas of Cu(1–6)(PPh3)2 (1a–6a) and Cu(1–6)(DPEphos) (1b–6b) [DPEphos = bis(2-diphenylphosphinophenyl)ether] all exhibit a pseudo-tetrahedral geometry, while complex Cu(7)(PPh3) (7a) is tricoordinated in a pyramidal conformation due to the large steric hindrance of ligand 7. The oxidation potentials assigned to oxidations of Cu(I)–Cu(II) are extraordinarily low in the range of 0.36–1.02 V vs. Ag/AgCl compared with traditional [Cu(phen)(PP)]+ analogues. Their emission maxima range from 495 to 595 nm in dichloromethane at room temperature with quantum yields of 0.05–4.03% and lifetimes on the order of nanoseconds. Unlike the characteristic MLCT emission in cationic Cu(I) complexes, the emissions are assigned to the dipyrrin-centered intraligand charge transition (ILCT) based on the fact that the increased conjugation within the dipyrrinato anion leads to a weaker metal–ligand interaction, thus preventing the mixing of π orbitals of ligand and 3d orbitals of Cu(I) atom. This conclusion is also supported by electrochemical data and theoretical calculations.

  合成了一系列含有二吡咯甲川衍生物和膦混合配体的杂配位中性单核亚铜配合物，并用 1,3,7,9-四甲基二吡咯甲川(1)、5-苯基-1,3,7,9-四甲基二吡咯甲川(2)、2,8-二溴-1,3,7,9-四甲基二吡咯甲川(3)、1,9-二氯-5-苯基二吡咯甲川(4)、1,9-二溴-5-苯基二吡咯甲川(5)、5-(五氟苯基)-1,3,7,9-四甲基二吡咯甲川(6)和1,5,9-三苯基二吡咯甲川(7)进行了全面表征。这些配合物的中心Cu(I)原子通常具有伪四面体几何构型，通式为Cu(1~6)(PPh3)2(1a~6a)和Cu(1~6)(DPEphos)(1b~6b)[DPEphos=二(2-二苯基膦苯基)醚]，而配体7由于空间位阻较大，使得配合物Cu(7)(PPh3)(7a)表现出三角锥形的结构。与传统的[Cu(phen)(PP)]+类似物相比，这些配合物中Cu(I)到Cu(II)的氧化电位在0.36至1.02 V(vs. Ag/AgCl)的范围内异常低。它们在室温下的二氯甲烷中的最大发射波长范围为495至595 nm，量子产率为0.05至4.03%，寿命为纳秒级。与阳离子Cu(I)配合物中的特征MLCT发射不同，这些配合物的发射被归因于二吡咯甲川中心的配体内电荷跃迁(ILCT)，这是因为二吡咯甲川阴离子内部共轭程度的增加导致金属与配体之间的相互作用减弱，从而阻止了配体π轨道与Cu(I)原子的3d轨道的混合。这一结论也得到了电化学数据和理论计算的支持。
• PHOTOELECTRIC CONVERSION ELEMENT, OPTICAL SENSOR, AND IMAGING ELEMENT
  申请人：FUJIFILM Corporation

  公开号：US20200035932A1

  公开（公告）日：2020-01-30

  The present invention provides a photoelectric conversion element exhibiting excellent responsiveness, and excellent dark current characteristics in a case of high-speed photoelectric conversion film formation, an optical sensor, an imaging element, and a compound which include the photoelectric conversion element. The photoelectric conversion element of the present invention includes a conductive film, a photoelectric conversion film, and a transparent conductive film, in this order, in which the photoelectric conversion film contains a compound represented by Formula (1), and an n-type organic semiconductor having a predetermined structure.

  本发明提供了一种光电转换元件，其在高速光电转换薄膜形成的情况下表现出优异的响应性和优秀的暗电流特性，以及包括该光电转换元件的光学传感器、成像元件和化合物。本发明的光电转换元件包括一个导电膜、一个光电转换膜和一个透明导电膜，按照这个顺序排列，其中光电转换膜含有一个由式（1）表示的化合物和一个具有预定结构的n型有机半导体。
• Spectroscopic, computational modeling and cytotoxicity of a series of meso-phenyl and meso-thienyl-BODIPYs
  作者：Jaime H. Gibbs、Larry T. Robins、Zehua Zhou、Petia Bobadova-Parvanova、Michael Cottam、Gregory T. McCandless、Frank R. Fronczek、M. Graça H. Vicente

  DOI：10.1016/j.bmc.2013.07.017

  日期：2013.9

  A series of twenty-two BODIPY compounds were synthesized, containing various meso-phenyl and meso-thienyl groups, and their spectroscopic and structural properties were investigated using both experimental and computational methods. Further functionalization of the BODIPY framework via iodination at the 2,6-pyrrolic positions was explored in order to determine the effect of these heavy atoms on the photophysical and cytotoxicity of the meso-aryl-BODIPYs. BODIPYs bearing meso-thienyl substituents showed the largest red-shifted absorptions and emissions and reduced fluorescence quantum yields. The phototoxicity of the BODIPYs in human carcinoma HEp2 cells depends on both the presence of iodines and the nature of the meso-aryl groups. Six of the eleven 2,6-diiodo-BODIPYs investigated showed at least a sevenfold enhancement in phototoxicity (IC50 = 3.5-28 mu M at 1.5 J/cm(2)) compared with the non-iodinated BODIPYs, while the others showed no cytotoxicity, while their singlet oxygen quantum yields ranged from 0.02 to 0.76. Among the series investigated, BODIPYs 2a and 4a bearing electron-donating meso-dimethoxyphenyl substituents showed the highest phototoxicity and dark/phototoxicity ratio, and are therefore the most promising for application in PDT. (C) 2013 Elsevier Ltd. All rights reserved.
• Synthesis and photo-physical properties of a series of BODIPY dyes
  作者：Stefano Banfi、Gianluca Nasini、Stefano Zaza、Enrico Caruso

  DOI：10.1016/j.tet.2013.04.064

  日期：2013.6

  A series of 39 boron-dipyrrolylmethenes (BODIPYs) have been synthesized and characterized. Their spectroscopic properties, degree of lipophilicity, chemical stability under irradiation, and singlet-oxygen generation rate have also been studied. These compounds differ in the presence of ethyl groups (group A), hydrogens (group B) or iodines (group C) on the 2,6 positions; these appendices confer particular characteristics to each group. The presence of an aromatic substituent or hydrogen on the indacene 8 position produces 13 different molecules of each group. Besides the effects exerted by the group or atom on the 2,6 positions, the substituent on the 8 position exerts a further effect on the physico-chemical parameters, thus the desired properties of BODIPYs, concerning fluorescence, lipophilicity, and singlet oxygen production can be modulated accordingly. (C) 2013 Elsevier Ltd. All rights reserved.