(E,E′)-4,4′-bis[p-(N,N-dimethylamino)styryl]-2,2′-bipyridine | 166827-54-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (E,E′)-4,4′-bis[p-(N,N-dimethylamino)styryl]-2,2′-bipyridine
• 英文别名: 4,4'-Bis[2-(4-N,N-dimethylaminophenyl)ethenyl]-2,2'-bipyridine；4-[(E)-2-[2-[4-[(E)-2-[4-(dimethylamino)phenyl]ethenyl]pyridin-2-yl]pyridin-4-yl]ethenyl]-N,N-dimethylaniline
• CAS: 166827-54-9
• 化学式: C₃₀H₃₀N₄
• 分子量: 446.595
• InChiKey: XYKUGOYLBPMTEK-KQQUZDAGSA-N

物化性质

• 沸点：
  667.2±55.0 °C(Predicted)
• 密度：
  1.164±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  32.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  水合三氯化钌 、 (E,E′)-4,4′-bis[p-(N,N-dimethylamino)styryl]-2,2′-bipyridine 在 hydroquinone 、 LiCl 作用下， 以 乙醇 为溶剂， 生成 [Ru((E,E′)-4,4′-bis[p-(N,N-dimethylamino)styryl]-2,2′-bipyridine)2Cl2]
  参考文献：
  名称：

  Influence of the Nature of the Absorption Band on the Potential Performance of High Molar Extinction Coefficient Ruthenium(II) Polypyridinic Complexes As Dyes for Sensitized Solar Cells

  摘要：

  When tested in solar cells, ruthenium polypyridinic dyes with extended pi systems show an enhanced light-harvesting capacity that is not necessarily reflected by a high (collected electrons)/(absorbed photons) ratio. Provided that metal-to-ligand charge transfer bands, MLCT, are more effective, due to their directionality, than intraligand (IL) pi-pi* bands for the electron injection process in the solar cell, it seems important to explore and clarify the nature of the absorption bands present in these types of dyes. This article aims to elucidate if all the absorbed photons of these dyes are potentially useful in the generation of electric current. In other words, their potentiality as dyes must also be analyzed from the point of view of their contribution to the generation of excited states potentially useful for direct injection. Focusing on the assignment of the absorption bands and the nature of the emitting state, a systematic study for a series of ruthenium complexes with 4,4'-distyryl-2,2'-dipyridine (LH) and 4,4'-bis[p-(dimethylamino)-alpha-styryl]-2,2'-bipyridine (LNMe2) "chromophoric" ligands was undertaken. The observed experimental results were complemented with TDDFT calculations to elucidate the nature of the absorption bands, and a theoretical model was proposed to predict the available energy that could be injected from a singlet or a triplet excited state. For the series studied, the results indicate that the percentage of MLCT character to the anchored ligand for the lower energy absorption band follows the order [Ru(deebpy)(2)(LNMe2)](PF6)(2) > [Ru(deebpy)(2)(LH)] (PF6)(2) > [Ru(deebpy)(LH)(2)](PF6)(2), where deebpy is 4,4'-bis(ethoxycarbonyl)-2,2'-bipyridine, predicting that, at least from this point of view, their efficiency as dyes should follow the same trend.

  DOI：

  10.1021/ic1020862
• 作为产物：
  描述：

  4,4'-二甲基-2,2'-联吡啶 、 对二甲氨基苯甲醛 在 potassium tert-butylate 作用下， 以 二甲胺 为溶剂， 反应 20.5h， 以64%的产率得到(E,E′)-4,4′-bis[p-(N,N-dimethylamino)styryl]-2,2′-bipyridine
  参考文献：
  名称：

  合理设计用于1和2光子光动力疗法的钌配合物。

  摘要：

  近年来，针对癌症的光动力疗法（PDT）的使用受到越来越多的关注。但是，目前批准的光敏剂（PSs）的应用受到水溶性差，聚集，光致漂白和从体内清除缓慢的限制。为了克服这些局限性，需要开发新型的带有钌（II）聚吡啶配合物的新型聚苯乙烯。然而，这些化合物通常在生物光谱窗口中缺乏明显的吸收，从而限制了它们在治疗深部或大肿瘤中的应用。为克服此缺点，在计算机上设计了具有（E，E的钌（II）聚吡啶络合物'）-4,4'-双苯乙烯基-2,2'-联吡啶配体显示出令人印象深刻的1和2光子吸收率，其幅度比迄今为止公布的值高。尽管这些化合物在黑暗中无毒，但它们在各种2D单层细胞，3D多细胞肿瘤球体中具有光毒性，并在临床相关的1-Photon和2-Photon激发下能够根除小鼠模型内的多抗性肿瘤。

  DOI：

  10.1038/s41467-020-16993-0

文献信息

• Rationally designed ruthenium complexes for 1- and 2-photon photodynamic therapy
  作者：Johannes Karges、Shi Kuang、Federica Maschietto、Olivier Blacque、Ilaria Ciofini、Hui Chao、Gilles Gasser

  DOI：10.1038/s41467-020-16993-0

  日期：——

  The use of photodynamic therapy (PDT) against cancer has received increasing attention over recent years. However, the application of the currently approved photosensitizers (PSs) is limited by their poor aqueous solubility, aggregation, photobleaching and slow clearance from the body. To overcome these limitations, there is a need for the development of new classes of PSs with ruthenium(II) polypyridine

  近年来，针对癌症的光动力疗法（PDT）的使用受到越来越多的关注。但是，目前批准的光敏剂（PSs）的应用受到水溶性差，聚集，光致漂白和从体内清除缓慢的限制。为了克服这些局限性，需要开发新型的带有钌（II）聚吡啶配合物的新型聚苯乙烯。然而，这些化合物通常在生物光谱窗口中缺乏明显的吸收，从而限制了它们在治疗深部或大肿瘤中的应用。为克服此缺点，在计算机上设计了具有（E，E的钌（II）聚吡啶络合物'）-4,4'-双苯乙烯基-2,2'-联吡啶配体显示出令人印象深刻的1和2光子吸收率，其幅度比迄今为止公布的值高。尽管这些化合物在黑暗中无毒，但它们在各种2D单层细胞，3D多细胞肿瘤球体中具有光毒性，并在临床相关的1-Photon和2-Photon激发下能够根除小鼠模型内的多抗性肿瘤。
• [EN] METAL COMPLEXES BEARING BISSTYRYL-BIPYRIDINE LIGAND AND THEIR USE AS PHOTOSENSITIZER AGENT IN ONE AND TWO-PHOTON PHOTODYNAMIC THERAPY<br/>[FR] COMPLEXES MÉTALLIQUES PORTANT UN LIGAND BISSTYRYL-BIPYRIDINE ET LEUR UTILISATION EN TANT QU'AGENT PHOTOSENSIBILISANT DANS UNE THÉRAPIE PHOTODYNAMIQUE À UN ET DEUX PHOTONS
  申请人：PARIS SCIENCES LETTRES QUARTIER LATIN

  公开号：WO2021089644A1

  公开（公告）日：2021-05-14

  The present invention relates to metal complexes bearing at least one (E-E')-4,4'- bisstyryl-2,2'-bipyridine ligand (LIG1) of the following formula (I): or a pharmaceutically acceptable salt and/or solvate thereof. The present invention also relates to pharmaceutical compositions comprising these complexes and at least one pharmaceutically acceptable excipient. The present invention also relates to the use of compounds of formula (I) or pharmaceutical compositions comprising thereof as drug and as photosensitizer agent in photodynamic therapy. The present invention also relates to methods of preparation of said complexes.

  本发明涉及具有至少一个(E-E')-4,4'-双亚基苯基-2,2'-联吡啶配体（LIG1）的金属配合物的以下结构式（I）：或其药学上可接受的盐和/或溶剂。本发明还涉及包括这些配合物和至少一种药学上可接受的赋形剂的制药组合物。本发明还涉及将结构式（I）的化合物或包含其的制药组合物用作药物和光动力疗法中的光敏剂的用途。本发明还涉及所述配合物的制备方法。
• Synthesis, Characterisation and Biological Evaluation of π-Extended Fe(II) Bipyridine Complexes as Potential Photosensitizers for Photodynamic Therapy
  作者：Johannes Karges、Gilles Gasser

  DOI：10.1016/j.ica.2019.119196

  日期：2020.1

  Photodynamic therapy (PDT) has received increasing attention over the recent years to treat a variety of cancers. The use of metal complexes as PDT agents is currently a highly investigated alternative due to the attractive chemical and photophysical properties of these compounds. However, most of the metal complexes studied so far are based on rare metals, limiting their use since these metals are neither cheap nor abundant. It would be therefore of high interest to develop compounds based on a cheap, abundant metal. Having this in mind, we designed Fe(II) polypyridine complexes with an absorption in the biological spectral window (600-900 nm) through extension of the pi-system. Importantly, the complexes were found to be stable in human plasma and upon light irradiation. A cytotoxic effect in the micromolar range in the dark and a slight effect upon exposure to irradiation at 480 and 540 nm in cancerous human cervical carcinoma (HeLa) cells was observed.
• One‐ and Two‐Photon Phototherapeutic Effects of Ru ^II Polypyridine Complexes in the Hypoxic Centre of Large Multicellular Tumor Spheroids and Tumor‐Bearing Mice**
  作者：Johannes Karges、Shi Kuang、Yih Ching Ong、Hui Chao、Gilles Gasser

  DOI：10.1002/chem.202003486

  日期：2021.1.4

  polypyridine complexes as one‐photon and two‐photon PSs. These metal complexes were found to fully penetrate the 3D cellular architecture and to generate singlet oxygen in the hypoxic center upon light irradiation. While having no observed dark toxicity, the lead compound of this study showed an impressive phototoxicity upon clinically relevant one‐photon (595 nm) or two‐photon (800 nm) excitation with

  在过去的几十年中，光动力疗法（PDT）是一种批准的医学技术，在治疗某些类型的癌症方面受到越来越多的关注。尽管最近有改进，但是由于光敏剂（PS）穿透3D细胞结构的能力低以及肿瘤中心存在的低氧浓度，大肿瘤的治疗仍然是临床上的主要挑战。为了模拟临床肿瘤中发现的疾病，这项工作中使用了直径为800μm的超大型3D多细胞肿瘤球体（MCTS），以测试一系列新型Ru II多吡啶复合物为单光子和双光子PS。发现这些金属络合物完全穿透3D细胞结构并在光照射下在低氧中心产生单线态氧。尽管没有观察到暗毒性，但这项研究的先导化合物在临床相关的单光子（595 nm）或双光子（800 nm）激发下显示出令人印象深刻的光毒性，并完全消除了MCTS的低氧中心。重要的是，这种功效还在携带腺癌人类肺泡基底上皮肿瘤的小鼠身上得到了证实。
• Influence of the Nature of the Absorption Band on the Potential Performance of High Molar Extinction Coefficient Ruthenium(II) Polypyridinic Complexes As Dyes for Sensitized Solar Cells
  作者：Francisco Gajardo、Mauricio Barrera、Ricardo Vargas、Irma Crivelli、Barbara Loeb

  DOI：10.1021/ic1020862

  日期：2011.7.4

  When tested in solar cells, ruthenium polypyridinic dyes with extended pi systems show an enhanced light-harvesting capacity that is not necessarily reflected by a high (collected electrons)/(absorbed photons) ratio. Provided that metal-to-ligand charge transfer bands, MLCT, are more effective, due to their directionality, than intraligand (IL) pi-pi* bands for the electron injection process in the solar cell, it seems important to explore and clarify the nature of the absorption bands present in these types of dyes. This article aims to elucidate if all the absorbed photons of these dyes are potentially useful in the generation of electric current. In other words, their potentiality as dyes must also be analyzed from the point of view of their contribution to the generation of excited states potentially useful for direct injection. Focusing on the assignment of the absorption bands and the nature of the emitting state, a systematic study for a series of ruthenium complexes with 4,4'-distyryl-2,2'-dipyridine (LH) and 4,4'-bis[p-(dimethylamino)-alpha-styryl]-2,2'-bipyridine (LNMe2) "chromophoric" ligands was undertaken. The observed experimental results were complemented with TDDFT calculations to elucidate the nature of the absorption bands, and a theoretical model was proposed to predict the available energy that could be injected from a singlet or a triplet excited state. For the series studied, the results indicate that the percentage of MLCT character to the anchored ligand for the lower energy absorption band follows the order [Ru(deebpy)(2)(LNMe2)](PF6)(2) > [Ru(deebpy)(2)(LH)] (PF6)(2) > [Ru(deebpy)(LH)(2)](PF6)(2), where deebpy is 4,4'-bis(ethoxycarbonyl)-2,2'-bipyridine, predicting that, at least from this point of view, their efficiency as dyes should follow the same trend.