meso-(n-heptyl)-2,2'-dipyrromethane | 352670-53-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: meso-(n-heptyl)-2,2'-dipyrromethane
• 英文别名: meso-heptyl-2,2'-dipyrrylmethane；meso-(n-heptyl)dipyrromethane；n-heptyldipyrromethane；meso-(n-heptyl)dipyromethane；2-[1-(1H-pyrrol-2-yl)octyl]-1H-pyrrole
• CAS: 352670-53-2
• 化学式: C₁₆H₂₄N₂
• 分子量: 244.38
• InChiKey: CVRYOCXJDUPNEX-UHFFFAOYSA-N

物化性质

• 沸点：
  407.6±25.0 °C(Predicted)
• 密度：
  1.010±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  31.6
• 氢给体数：
  2
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  meso-(n-heptyl)-2,2'-dipyrromethane 在 zinc diacetate 、 三氟乙酸 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 3.0h， 生成 5,10,15-tris(n-heptyl)-20-(2'-bromo-4'-pyridyl)porphyrinatozinc
  参考文献：
  名称：

  Synthesis of Bipyridylene-Bridged Bisporphyrin by Nickel-Mediated Coupling Reaction:  ON−OFF Control of Cofacial Porphyrin Unit by Reversible Complexation

  摘要：

  Novel bipyridylene-bridged bisporphyrin la, in which two porphyrin units were attached directly to symmetrical 4,4'-positions of the 2,2'-bipyridyl group, was synthesized by a nickel(0)-mediated homocoupling reaction of 5,10,15-tris(n-heptyl)-20-(2'-bromo-4'-pyridyl)porphyrinatozinc (3a) in 58% yield. Spatial geometries of two porphyrins in la were regulated by reversible complexation of the bipyridyl part with PdCl(2). Thus, the addition of 2.2 equiv of palladium chloride to la converted the freely rotating conformation to the cofacial bisporphyrin 2a. The subsequent addition of 4,4'-dimethyl-2,2'-bipyridine 9 regenerated the initial bisporphyrin 1a.

  DOI：

  10.1021/jo015852b
• 作为产物：
  描述：

  吡咯 、 正辛醛 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以38%的产率得到meso-(n-heptyl)-2,2'-dipyrromethane
  参考文献：
  名称：

  大环卟啉六聚体和星形卟啉阵列之间的超分子组装。

  摘要：

  八个新的星形D（3）对称阵列的合成，其中三个15-（吡啶-4-基）卟啉亚基通过由共线重复的连接子连接到苯核的1、3和5位苯乙炔基单元已使用Pd（0）催化的偶联反应进行。通过相同的步骤，获得了类似的10-（4-吡啶基-基）卟啉六聚体，其中苯核的所有位置均被取代。同样，详细描述了适当大小的环状卟啉六聚物的制备，其中所有六个或至少三个交替的卟啉环均与Zn（II）离子络合。在解决方案中，这种环状卟啉六聚体与星形聚卟啉形成超分子组装，其中星形聚卟啉通过顶端吡啶环与Zn（II）离子的配位而保持在大环的内部。所建议的结构由（1）H NMR光谱和MALDI-TOF质谱测量支持。它们与相应的超分子的结合常数的高值一致，其范围在K = 1.1 x 10（10）和1.4 x10（9）M（-1）之间。

  DOI：

  10.1021/jo0015523

文献信息

• Hexameric Macroring of Gable-Porphyrins as a Light-Harvesting Antenna Mimic
  作者：Ryoichi Takahashi、Yoshiaki Kobuke

  DOI：10.1021/ja028325y

  日期：2003.3.1

  Construction of a self-assembled supramolecular macroring that has distances and orientations of porphyrin dimer units in close analogy to those of the natural light-harvesting complexes was achieved. In natural light-harvesting complexes, bacteriochlorophyll-a's are arranged in macroring structures by coordination from imidazolyl side chains. A structural determination of a light-harvesting antenna

  实现了自组装超分子大环的构建，该大环的卟啉二聚体单元的距离和方向与自然光捕获复合物的距离和方向非常相似。在天然捕光复合物中，细菌叶绿素-a 通过咪唑基侧链的配位排列在大环结构中。1995 年，光捕获天线复合物 (LH2) 的结构测定阐明了 18 个细菌叶绿素 a 以滑动共面方式排列，并在 1995 年在 B850 中具有 C9 对称性。为了获得如此优雅的宏环结构作为人工光捕获复合物，我们以山墙卟啉方向连接了咪唑基卟啉的滑动共面二聚体。引入由配位卟啉组装而成的锌，最初具有较宽的分子量分布 (MWD)。当使用氯仿/甲醇溶液在高稀释条件下裂解和重组配位键时，MWD 完全收敛。这种作物通过原子力显微镜测量给出了均匀高度的粒子图像。通过凝胶渗透色谱成功地实现了进一步的纯化，第一个洗脱组分的直径与同步辐射的小角 X 射线散射测量结果对应于山墙卟啉的环状六聚体。总之，大环排列中的卟啉组件是使用山墙卟啉基
• Role of the Special Pair in the Charge-Separating Event in Photosynthesis
  作者：Hidekane Ozeki、Akihiro Nomoto、Kazuya Ogawa、Yoshiaki Kobuke、Masataka Murakami、Kou Hosoda、Masana Ohtani、Satoru Nakashima、Hiroshi Miyasaka、Tadashi Okada

  DOI：10.1002/chem.200400624

  日期：2004.12.17

  complementary slipped cofacial dimer of imidazolyl-substituted zinc porphyrin, bearing pyromellitdiimide as the electron acceptor. In the case of the dimer, the first and second oxidation potentials were split into a total of four peaks in the differential pulse voltammetry measurement. Furthermore, the shift values of the first oxidation potentials obtained by changing the solvent polarity for the dimer were

  我们合成了特殊对/电子受体体系，该体系由咪唑基取代的锌卟啉的互补滑面二聚体组成，并以均苯四甲二酰亚胺为电子受体。在二聚体的情况下，在差分脉冲伏安法测量中，第一和第二氧化电位被分成总共四个峰。此外，通过改变二聚体的溶剂极性获得的第一氧化电位的位移值几乎是单体观察到的位移值的一半。这些结果表明自由基阳离子在二聚体的整个π系统上是离域的。时间分辨的瞬态吸收测量结果表明，相对于相应的单体，二聚体加快了电荷分离速率，但降低了电荷复合速率。
• Porphyrin array exhibiting large two photon absorption property and including, as structural unit, bis(imidazolylporphyrin metal complex) linked with acetylenic bond and the derivative thereof, and method of producing the same
  申请人：——

  公开号：US20040106787A1

  公开（公告）日：2004-06-03

  A porphyrin array exhibiting a large two-photon absorption property, and being linked with an acetylenic bond(s), represented by the following formulas: 1 wherein R 1 represents an alkyl or aryl group, M 1 represents a metal ion capable of serving as a core metal and forming a coordinate bond with Im, M 2 represents two protons or a metal ion incapable of forming a coordinate bond with Im, R 2 and R 3 represent a group selected from a porphyrin residue or porphyrin metal complex residue, a cyclic diimide residue, a dialkylviologen residue, a benzoquinone residue, an N-methylpyrrolidine-fullerene derivative residue and a ferrocene residue, Im is represented by Im 1 or Im 2 : 2 (R 8 represents methyl or H), L 1 represents —(—C≡C—) m — (m=1 to 3); n represents an integer of 1 or more; R 9 represents one of R 1 , R 2 , R 3 and Im.

  具有大的双光子吸收性质并与乙炔键连接的卟啉阵列，由以下公式表示： 其中，R1表示烷基或芳基基团，M1表示能够作为核心金属并与Im形成配位键的金属离子，M2表示两个质子或无法与Im形成配位键的金属离子，R2和R3表示从卟啉残基或卟啉金属配合物残基、环状二亚胺残基、双烷基吡啶残基、苯醌残基、N-甲基吡咯烷-富勒烯衍生物残基和二茂铁残基中选择的基团，Im由Im1或Im2表示：2（R8表示甲基或H），L1表示—（—C≡C—）m—（m=1至3）；n表示1或更多的整数；R9表示R1、R2、R3和Im中的一个。
• Coordination Assembled Rings of Ferrocene-Bridged Trisporphyrin with Flexible Hinge-like Motion:  Selective Dimer Ring Formation, Its Transformation to Larger Rings, and Vice Versa
  作者：Osami Shoji、Saori Okada、Akiharu Satake、Yoshiaki Kobuke

  DOI：10.1021/ja0445746

  日期：2005.2.1

  Ferrocene-bridged trisporphyrin (2) was synthesized by two-steps condensation of corresponding aldehydes and dipyrromethanes, and its self-assembling behavior based on the complementary coordination motif of imidazolylporphyrinatozinc(II) was investigated in conjunction with hinge-like flexibility given by freely rotating cyclopentadienyl rings of ferrocene connector. Ferrocene-bridged trisporphyrin (2) spontaneously and exclusively generated the dimeric ring (7) upon simple zinc(II) insertion, indicating that the freely rotating hinge connector favored the smallest ring formation. Taking advantage of the unique hinge-like flexibility of ferrocene, we attempted to transform the dinner ring into a mixture of porphyrin macrocycles by reorganizing the structure cleaved once by pyridine. A series of porphyrin macrocycles from trimer to decamer can be separated into its components by preparative gel permeation chromatograms. Macrocycles obtained are kept stable in the absence of coordinating solvents. On the other hand, they were easily transformed to the dimer ring in the presence of coordinating solvents such as methanol, showing that the transformation is completely reversible and can be controlled by the choice of the solvent system. A series of porphyrin macrocycles was confirmed via covalent linking of each complementary coordination dinner pair by metathesis reaction in the presence of Grubbs's catalyst. The coordination behavior of the bidentate ligands with different spacer lengths toward the dimer ring revealed that only the bidentate ligand (15) with a spacer length that matched the facing central porphyrins was selectively accommodated inside the ring. Coordination assembled flexible rings with tunable cavities and multiple coordination sites will be used as versatile hosts for a wide variety of guest molecules.
• Strong Two-Photon Absorption of Self-Assembled Butadiyne-Linked Bisporphyrin
  作者：Kazuya Ogawa、Atsushi Ohashi、Yoshiaki Kobuke、Kenji Kamada、Koji Ohta

  DOI：10.1021/ja035056i

  日期：2003.11.1

  Two-photon absorption (2PA) properties of self-assembled porphyrins were investigated. The butadiyne-linked porphyrin array exhibited a 20 times larger 2PA cross section than the meso-meso-linked self-assembled array due to the expansion of pi-conjugation. Higher-order nonlinear absorption was also observed in the former porphyrin.