7,17-Bis(2,4,6-trimethylphenyl)-2,12,21,23-tetraza-22,24-diazanidapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1(21),2,4,6,8(23),9,11,13,15,17,19-undecaene;nickel(2+) | 1378531-49-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 7,17-Bis(2,4,6-trimethylphenyl)-2,12,21,23-tetraza-22,24-diazanidapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1(21),2,4,6,8(23),9,11,13,15,17,19-undecaene;nickel(2+)
• CAS: 1378531-49-7
• 化学式: C₃₆H₃₀N₆Ni
• 分子量: 605.364
• InChiKey: NOKDNINNPFFVHC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  7,17-Bis(2,4,6-trimethylphenyl)-2,12,21,23-tetraza-22,24-diazanidapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1(21),2,4,6,8(23),9,11,13,15,17,19-undecaene;nickel(2+) 在 N-溴代丁二酰亚胺(NBS) 作用下， 生成 3-bromo-NiDAP
  参考文献：
  名称：

  吡咯和噻吩桥联的5,15-二氮杂卟啉二聚体的光学，电化学和磁性

  摘要：

  吡咯和噻吩桥连的5,15-二氮杂卟啉（DAP）二聚体的第一个实例是通过3-溴10,20-二甲磺酰基1-5,15的镍（II）和铜（II）配合物的Stille偶联反应制备的-重氮杂卟啉（1,2,4,6-三甲基苯基）与各自的2,5-双（三丁基锡烷基）杂环。杂化间隔基和内消旋的影响通过UV / Vis吸收光谱，密度泛函理论计算，磁性圆二色光谱，循环伏安法和EPR光谱研究了DAP二聚体的光学，电化学和磁性性质上的氮原子。发现杂环间隔物对整个π系统上的电子跃迁有重大影响。尤其是，由于最低激发的固有电荷转移特性，吡咯桥式DAP二聚体在低能可见光/近红外区域表现出较高的集光潜力。

  DOI：

  10.1002/chem.201405482

文献信息

• Comparison of electronic effects of β-aryl substituents on optical and electrochemical properties of 5,15-diazaporphyrin π-systems
  作者：Satoshi Omomo、Ko Furukawa、Haruyuki Nakano、Yoshihiro Matano

  DOI：10.1142/s1088424615500509

  日期：2015.6

  The syntheses and optical/electrochemical properties of 3-aryl-10,20-dimesityl-5,15-diazaporphyrin-metal complexes (MDAPs; mesityl = 2,4,6-trimethylphenyl; M = Ni , Zn ) are reported. Treatment of 3-bromo-MDAPs with arylboronic acids in the presence of a Pd catalyst and a bulky phosphine ligand in a dioxane-water mixed solvent afforded the corresponding 3-aryl-MDAPs in moderate to good yields. X-ray crystallographic analysis of p- EtO ₂ CC ₆ H ₄- NiDAP showed that the β-aryl group was tilted toward the NiDAP ring, with a dihedral angle of 21.7°. In the UV-visible absorption spectra, all the Ar-MDAPs showed intense Q-bands attributable to HOMO-to-LUMO transitions. The para substituents were found to influence the HOMO energies, which eventually resulted in fine tuning of the HOMO–LUMO gaps of the diazaporphyrin chromophores. It is worth noting that the p- Ph ₂ NC ₆ H ₄- ZnDAP showed broad absorption and emission bands in the visible-near-infrared regions. The large Stokes shifts and their linear solvation energy relationships vs. orientation polarizability show that this Ph ₂ N -substituted derivative has intrinsically high charge transfer from the triphenylamine (donor) to the ZnDAP (acceptor) unit. These experimental observations were supported by theoretical calculations for model Ar-ZnDAP compounds. These results confirm that the introduction of a highly electron-donating aryl group at the peripheral β-carbon is a promising strategy for enhancing the light-harvesting and light-emitting abilities of diazaporphyrin-based π-systems in the visible-near-infrared regions.

  报告了 3-芳基-10,20-二甲基-5,15-二氮杂卟啉金属配合物（MDAPs；mesityl = 2,4,6-三甲基苯基；M = Ni , Zn）的合成和光学/电化学性质。在二噁烷-水混合溶剂中，在钯催化剂和笨重的膦配体存在下，用芳基硼酸处理 3-溴-MDAPs，得到了相应的 3-芳基-MDAPs，收率中等至良好。对 p- EtO 2 CC 6 H 4- NiDAP 的 X 射线晶体分析表明，β 芳基向 NiDAP 环倾斜，二面角为 21.7°。在紫外-可见吸收光谱中，所有 Ar-MDAP 都显示出强烈的 Q 带，这是由于 HOMO 到 LUMO 的跃迁。研究发现，对位取代基会影响 HOMO 能量，最终导致重氮卟啉发色团的 HOMO-LUMO 间隙发生微调。值得注意的是，对位 Ph 2 NC 6 H 4 ZnDAP 在可见光和近红外区域显示出宽广的吸收和发射带。巨大的斯托克斯偏移及其线性溶解能与取向极化性的关系表明，这种 Ph 2 N 取代衍生物具有从三苯胺（供体）到 ZnDAP（受体）单元的内在高电荷转移。这些实验观察结果得到了 Ar-ZnDAP 模型化合物理论计算的支持。这些结果证实，在外围的 β 碳上引入高电子供体芳基是一种很有前途的策略，可以增强重氮卟啉基 π 系统在可见光和近红外区域的光收集和发光能力。
• Covalently Linked 5,15-Diazaporphyrin Dimers: Promising Scaffolds for a Highly Conjugated Azaporphyrin π System
  作者：Yoshihiro Matano、Daisuke Fujii、Tarou Shibano、Ko Furukawa、Tomohiro Higashino、Haruyuki Nakano、Hiroshi Imahori

  DOI：10.1002/chem.201304626

  日期：2014.3.17

  The first examples of β–β directly linked, acetylene‐bridged, and butadiyne‐bridged 5,15‐diazaporphyrin dimers have been prepared by palladium‐catalyzed coupling reactions of nickel(II) and copper(II) complexes of 3‐bromo‐10,20‐dimesityl‐5,15‐diazaporphyrin (mesityl=2,4,6‐trimethylphenyl). The effects of the linking modes and meso‐nitrogen atoms on the structural, optical, electrochemical, and magnetic

  β-β的所述第一实例直接连接，乙炔桥接，和丁二炔桥接5,15- diazaporphyrin二聚体已经制备通过钯催化的偶联镍（II）和铜（II）的3-溴- 10复合物的反应，20-二甲磺酰基-1,5,15-二氮杂卟啉（甲磺酰基= 2,4,6-三甲基苯基）。链接模式和的影响内消旋通过使用X射线晶体学，紫外/可见光吸收光谱，DFT计算，循环伏安法，和ESR的分布式π系统的结构，光学，电化学，和磁特性-氮原子进行了研究光谱。无论是电子和空间位阻效应观 - 氮原子起到直接连接的二聚体的高度共面的几何形状具有重要作用。直接β-β键产生增强的π共轭和电子自旋两个diazaporphyrin单元之间的耦合。
• Carbolithiation of meso-aryl-substituted 5,15-diazaporphyrin selectively provides 3-alkylated diazachlorins
  作者：Ayaka Yamaji、Satoru Hiroto、Ji-Young Shin、Hiroshi Shinokubo

  DOI：10.1039/c3cc41907j

  日期：——

  Treatment of meso-mesityl 5,15-diazaporphyrin with alkyllithiums in toluene at low temperature provided monoalkylated diazachlorins through highly regioselective nucleophilic addition at the β-position near the meso-nitrogen atom.

  在低温条件下，用烷基锍在甲苯中处理介甲基 5,15-二氮杂卟啉，通过在介氮原子附近的 β 位进行高区域选择性亲核加成，制备出单烷基二氮杂卟啉。
• Chemo- and Regioselective Reduction of 5,15-Diazaporphyrins Providing Antiaromatic Azaporphyrinoids
  作者：Ayaka Yamaji、Hayato Tsurugi、Yoshihiro Miyake、Kazushi Mashima、Hiroshi Shinokubo

  DOI：10.1002/chem.201600066

  日期：2016.3.14

  Reagent‐controlled chemo‐ and regioselective reduction of 5,15‐diazaporphyrins has been developed. The selective reduction of carbon–carbon double bonds of diazaporphyrins provides 18 π aromatic isobacteriochlorin‐type products, whereas the reduction of carbon–nitrogen double bonds leads to selective formation of 20 π N,N′‐dihydrodiazaporphyrins in excellent yields. The distinct antiaromatic character

  已经开发了通过试剂控制的5,15-二氮杂卟啉的化学和区域选择性还原反应。的diazaporphyrins的碳-碳双键的选择性还原提供18π芳香族isobacteriochlorin型产品，而碳-氮双键的引线的还原到π20的选择性形成Ñ，Ñ以优良产率'-dihydrodiazaporphyrins。N，N′-二氢二氮杂卟啉具有独特的抗芳香特性。与相应的18π卟啉相比，游离碱N，N'-二氢二氮杂卟啉显示出更慢的内部NH互变异构现象。
• Direct and Regioselective Amination of β-Unsubstituted 5,15-Diazaporphyrins with Amines: A Convenient Route to Near-Infrared-Responsive Diazaporphyrin Sensitizers
  作者：Satoshi Omomo、Takuma Sugai、Mao Minoura、Haruyuki Nakano、Yoshihiro Matano

  DOI：10.1002/anie.201800471

  日期：2018.3.26

  for the base‐promoted direct amination of β‐unsubstituted 5,15‐diazaporphyrins (DAPs) with secondary and primary amines to produce 3,7,13,17‐tetraamino‐ and 3‐amino‐DAPs, respectively, regioselectively. The amino groups attached at the periphery cause significant red shifts of the absorption bands as a result of their perturbation of the HOMO and/or LUMO in the DAP π‐system. The palladium complex of a

  我们已经建立了一种方便的方法，用于用仲胺和伯胺对β-未取代的5,15-二氮杂卟啉（DAP）进行碱促进的直接胺化，以分别生成3,7,13,17-四氨基-和3-氨基-DAP ，区域选择性地。由于在DAPπ系统中对HOMO和/或LUMO的扰动，连接在外围的氨基导致吸收带发生明显的红移。3,7,13,17-四（二苯基氨基）-DAP的钯配合物在近红外光照射下高产产生单线态氧。