2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato zinc(II) | 131214-88-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato zinc(II)
• 英文别名: zinc β-octabromo-meso-tetraphenylporphyrine；zinc(II) octabromotetraphenylporphyrinate；Zn(II) 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin
• CAS: 131214-88-5
• 化学式: C₄₄H₂₀Br₈N₄Zn
• 分子量: 1309.29
• InChiKey: JQAGRRGFAYYAQE-OEHKZIGDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.52
• 重原子数：
  57.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  53.98
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato zinc(II) 在 溶剂黄146 作用下， 以 溶剂黄146 为溶剂， 生成 锌
  参考文献：
  名称：

  Dissociation kinetics of cobalt and zinc β-octabromo-meso-tetraphenyl- and β-octaethyl-meso-tetraphenylporphyrin complexes

  摘要：

  Kinetics of solvoprotolytic dissociation of zinc and cobalt porphyrin complexes with a porphyrin macrocycle distorted to different extents (beta-octaethyl-meso-tetraphenylporphyrin and beta-octabromo-meso-tetraphenylporphyrin) have been studied in binary proton-donating solvents. The main factor decreasing the stability of the porphyrin complexes is the distortion of the planar structure of the macrocycle. The reactivity of the cobalt porphyrins is governed by both structural and electronic effects.

  DOI：

  10.1134/s0023158407020024
• 作为产物：
  描述：

  tetraphenylporphyrin 在 N-溴代丁二酰亚胺(NBS) 、 高氯酸 作用下， 以 氯仿 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 50.7h， 生成 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato zinc(II)
  参考文献：
  名称：

  β-溴化四苯基卟啉的配合物形成及其镉配合物与d-金属盐在二甲基甲酰胺中的金属交换

  摘要：

  与四苯基卟啉，2-溴-5,10,15,20-四苯基卟啉，2,3,12,13-四溴-5,10,15,20-四苯基卟啉和2的乙酸锌和乙酸铜（II）的络合物形成研究了N，N-二甲基甲酰胺中的3,7,8,12,13,17,18-八溴-5,10,15,20-四苯基卟啉。比较了在络合物形成和金属交换反应研究中确定的速率常数。

  DOI：

  10.1134/s1070363216010187

文献信息

• Design of oxophilic metalloporphyrins: an experimental and DFT study of methanol binding
  作者：Sandra Olsson、Christian Dahlstrand、Adolf Gogoll

  DOI：10.1039/c8dt02432d

  日期：——

  these results the optimal porphyrins can be selected for the desired binding interactions. We also show how to use DFT calculations to evaluate the potential binding between a metalloporphyrin and a ligand, which is deduced from free energies of binding ΔG, charge transfer ΔQ, and change of metal spin state. Computations on unsubstituted porphyrins in lieu of tetraphenyl porphyrin systems yield reliable

  通过系统的测量，我们以甲醇，乙酸和丙酮为例，评估了一系列四苯基金属卟啉和卤代四苯基金属卟啉衍生物与具有含氧官能团的配体的结合。实验结合常数确定了与所有三个配体（MgTPFPP，MgTPPBr 8和ZnTPPBr 8）具有良好结合的三种金属卟啉，以及一系列与所选配体结合的卟啉。基于这些结果，可以针对所需的结合相互作用选择最佳的卟啉。我们还展示了如何使用DFT计算来评估金属卟啉与配体之间的潜在结合，这是从结合自由能ΔG，电荷转移ΔQ推导而来的，以及金属自旋状态的变化。代替四苯基卟啉体系的未取代卟啉的计算可得出结合相互作用的可靠预测，并与相应的实验数据具有良好的相关性。该计算还产生了关于β位卤化对与含氧官能团的配体结合的影响的有趣见解。
• Effect of β-bromo substitution on the photophysical properties of<i>meso</i>-phenyl,<i>meso</i>-carbazole, and<i>meso</i>-triphenylamine porphyrins
  作者：Joy E. Haley、Weijie Su、Kristi M. Singh、Jennifer L. Monahan、Jonathan E. Slagle、Daniel G. McLean、Thomas M. Cooper

  DOI：10.1142/s1088424612500381

  日期：2012.4

  We present results of an experimental photophysical study of a series of novel brominated and non-brominated porphyrins that contain phenyl, carbazole, or triphenylamine in the meso-position. In addition we have looked at the effects of incorporating a zinc metal into the porphyrin system relative to the free base. Structure-property relationships are established using various absorption and emission techniques including femtosecond pump probe transient absorption and nanosecond laser flash photolysis. With slightly increasing electron donating strength (phenyl < carbazole < triphenylamine) red shifts were observed in all data. The same effect was observed upon the addition of bromine in the beta position. Due to the heavy atom affect of the bromines both the singlet and triplet excited state lifetimes were significantly shorter in the brominated porphyrins. For the T₁–T_nabsorption data we observe a large absorption in the near infrared region with the brominated carbazole and triphenylamine. The largest effect of the addition of zinc was in the ground state absorption and emission where a blue shift in the data was observed. Some effects were also observed in the kinetic decays with zinc as the metal compared to the free base porphyrins.

  我们展示了一系列新型溴化和非溴化卟啉的光物理实验研究结果，这些卟啉在中间位置含有苯基、咔唑或三苯胺。此外，我们还研究了在卟啉体系中加入金属锌对游离碱的影响。我们利用各种吸收和发射技术，包括飞秒泵浦探针瞬态吸收和纳秒激光闪烁光解技术，建立了结构与性质之间的关系。随着电子捐赠强度（苯基< 咔唑< 三苯胺）的略微增加，所有数据都出现了红移。在 beta 位置添加溴时，也观察到了同样的效果。由于溴的重原子效应，溴化卟啉的单线态和三线态激发态寿命都明显缩短。在 T1-Tnabsorption 数据中，我们观察到溴化咔唑和三苯胺在近红外区域有大量吸收。锌的加入对基态吸收和发射的影响最大，在基态吸收和发射中观察到数据发生了蓝移。与游离碱卟啉相比，在锌作为金属的动力学衰变中也观察到了一些影响。
• Perbrominated 2-nitrotetraphenylporphyrins: electrochemical and axial ligation properties
  作者：Puttaiah Bhyrappa、Bhavana Purushothaman

  DOI：10.1039/b003605f

  日期：——

  A new series of perbrominated 2-nitro-5,10,15,20-tetraphenylporphyrins, H2TPPBrn(NO2) (n = 6 and 7) and their metal (CuII and ZnII) complexes have been synthesised and characterised. The presence of mixed electron withdrawing (bromo- and nitro-) substituents at the β-pyrrole positions induces interesting electrochemical and axial ligation properties. Perbrominated nitroporphyrins exhibit two successive one electron redox potentials with a positive shift of >100 mV relative to their corresponding octabromotetraphenylporphyrin (MTPPBr8) complexes. Axial ligation of various nitrogenous bases to ZnTPPBrn(NO2) complexes showed facile ligand binding with >50% enhancement in the equilibrium constants, Keq, relative to ZnTPPBr8. Surprisingly, MTPPBrn(NO2) complexes show similar axial ligation and electrochemical redox behaviour. The anodic shift in electrochemical redox potentials and enhanced Keq of MTPPBrn(NO2) complexes have been attributed to the increased electron deficiency of the porphyrin π-system.

  我们合成了一系列新的过溴 2-硝基-5,10,15,20-四苯基卟啉 H2TPPBrn(NO2)（n = 6 和 7）及其金属（CuII 和 ZnII）配合物，并对其进行了表征。在 β-吡咯位置上存在的混合取电子（溴和硝基）取代基具有有趣的电化学和轴向连接特性。与相应的八溴四苯基卟啉（MTPPBr8）复合物相比，过溴化硝基卟啉表现出两个连续的单电子氧化还原电位，正移大于 100 mV。各种含氮碱基与 ZnTPPBrn( ) 复合物的轴向连接显示了配体结合的便利性，相对于 ZnTPPBr8，平衡常数 Keq 提高了 50%以上。令人惊讶的是，MTPPBrn( ) 复合物显示出类似的轴向连接和电化学氧化还原行为。MTPPBrn( ) 复合物电化学氧化还原电位的阳极移动和 Keq 的增强归因于卟啉 π 系统电子缺失的增加。
• Structure of Nonplanar Octabromotetraphenyl Porphyrin and Kinetics of Rapid Metalation Reactions
  作者：Puttaih Bhyrappa、Munirathinam Nethaji、Varadachari Krishnan

  DOI：10.1246/cl.1993.869

  日期：1993.5

  Octabromotetraphenylporphyrin adopts a severe saddle-shaped distorted structure owing to the steric crowding of heavy bromine substituents. The rate enhancement of porphyrin metalation reaction is primarily due to the nonplanarity of the ring while the electronic effect diminishes the affinity of the porphyrin towards metal ions.

  八溴四苯基卟啉由于重溴取代基的立体拥挤而形成了严重的马鞍形扭曲结构。卟啉金属化反应的速率提高主要是由于环的非平面性，而电子效应则降低了卟啉对金属离子的亲和力。
• Investigation of Acidic and Coordination Properties of Octabromo-Substituted Porphyrins in the System of 1,8-Diazabicyclo[5,4,0]unde-7-ene-Acetonitrile
  作者：S. G. Pukhovskaya、Yu. B. Ivanova、A. S. Semeikin、S. A. Syrbu、N. N. Kruk

  DOI：10.1134/s1070363219060252

  日期：2019.6

  are described for three porphyrin derivatives, different in their macrocycle conformation and electronic substitution effects due to bromine substitution in pyrrole rings and trifluorometyl or phenyl groups in meso-positions. Combination of these facts allows modulating both steric and electronic effects on the macrocycle π-conjugated system. The role of electronic substitution effects in the macrocycle

  描述了三种卟啉衍生物的酸度和金属离子配位，它们的大环构象和电子取代效应不同，这是由于吡咯环中的溴取代以及介位的三氟甲基或苯基所致。这些事实的结合允许调制对大环π共轭系统的空间和电子效应。发现电子取代效应在大环去质子化和金属离子络合物形成中的作用在可比较的共振和感应作用中占主导，而反应性物质的非平面构象在较小程度上对反应速率有贡献。两个单电子（a 1 u e g）和（a研究了三种三吡咯化合物分子结构的非平面畸变的函数2 u e g）。上的单电子（配置交互干扰因素的影响添加剂一个1 Ù Ë克）和（一个2 û ë克）在四吡咯大环化合物的结构是证明。