2-nitro-7,8,12,13,17,18-hexabromo-meso-tetraphenylporphyrinato copper(II) | 207236-03-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 2-nitro-7,8,12,13,17,18-hexabromo-meso-tetraphenylporphyrinato copper(II)
• 英文别名: CuTPP(NO2)Br6
• CAS: 207236-03-1
• 化学式: C₄₄H₂₁Br₆CuN₅O₂
• 分子量: 1194.65
• InChiKey: GUJXCWLJWBBADQ-QJTUXNKTSA-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：

  2-nitro-7,8,12,13,17,18-hexabromo-meso-tetraphenylporphyrinato copper(II) 在 硫酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以94%的产率得到2-nitro-7,8,12,13,17,18-hexabromo-meso-tetraphenylporphyrin
  参考文献：
  名称：

  2,3-二溴和2,3,7,8,12,13-六溴-5,10,15,20-四苯基卟啉的区域选择性合成和结构表征

  摘要：

  分别由H 2（2-NO 2 TPP）1和Cu（2-NO 2 TPP）8制备标题二溴卟啉和六溴卟啉。β-硝基将四苯基卟啉的18-π-环戊烯系统限制在其N 22 H -N 24 H芳香族离域路径上，该路径诱导对偶双键在卟啉外围上的定位并增强其对亲电攻击的敏感性。H 2 -NO 2 TPP）1的二溴化区域选择性地发生，从而提供12,13-二溴-2-硝基卟啉2其在迈克尔添加NaBH 4并将所得的硝基氯3重新芳构化后，提供了进入2,3-二溴TPP的途径以及改进的制备2,3-二氰基卟啉的途径。Cu（2-NO 2 TPP）8的全溴化和9的脱硝在脱金属后得到2,3,7,8,12,13-hexabromoTPP 12。两个4和12在结构上的特征在于X射线晶体学。

  DOI：

  10.1016/s0040-4020(99)00811-x
• 作为产物：
  描述：

  Cu(2+)-nitro-α,β,γ,δ-tetraphenylporphine 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 乙二胺 为溶剂， 反应 16.0h， 以81%的产率得到2-nitro-7,8,12,13,17,18-hexabromo-meso-tetraphenylporphyrinato copper(II)
  参考文献：
  名称：

  Synthesis, Spectral, and Electrochemical Studies of Electronically Tunable β-Substituted Porphyrins with Mixed Substituent Pattern

  摘要：

  Two new families of porphyrins with mixed substituent pattern, viz. 2-nitro-12,13-disubstituted-meso-tetraphenylporphyrins (H2TPP(NO2)X-2, X = Ph, phenylethynyl (PE), 2-thienyl (Th), Br, and CN) and 2-nitro-7,8,12,13,17,18-hexasubstituted-meso-tetraphenylporphyrins (H2TPP(NO2)X-6, X = Br, Ph, PE, and Th), and their metal (Co(II), Ni(II), Cu(II), and Zn(II)) complexes have been synthesized and characterized. H2TPP(NO2)X6 exhibited remarkable red shift in the Soret band (45-70 nm) and longest wavelength band, Qx(0,0) (65-90 nm), as compared to H2TPP(NO2). Single-crystal structures of MTPP(NO2)X-2 (M = Zn(II) and Ni(II); X = Br, Ph, and PE) showed quasi-planar conformation, whereas H2TPP(NO2)Th-2 and NiTPP(NO2)Br-6 exhibited moderate and highly nonplanar saddle-shape conformations, respectively. Further, DFT fully optimized geometries of H2TPP(NO2)X-2 and H2TPP(NO2)X-6 revealed moderate and severe saddle-shape nonplanar conformations, respectively. The imino proton resonances of H2TPP(NO2)X-6 are significantly downfield shifted (Delta delta = 1.10-1.80 ppm) relative to H2TPP(NO2). Mixed substituted highly nonplanar porphyrins exhibited higher protonation and deprotonation constants relative to H2TPPX8 (X = Cl and Br). The redox tunability was achieved by introducing electron donor (Ph and Th) and acceptor (PE, Br, and CN) groups on the MTPP(NO2) backbone. The unusual variation in the spectral and electrochemical redox properties of mixed substituted porphyrins are interpreted in terms of both an inductive and a resonance interaction of substituents on the porphyrin p-system as well as nonplanarity of the macrocycle.

  DOI：

  10.1021/ic501259g

文献信息

• Dodecasubstituted metallochlorins (metallodihydroporphyrins)
  作者：Kalyn M. Shea、Laurent Jaquinod

  DOI：10.1039/a708766g

  日期：——

  Regioselective bromination of 2-nitro-5,10,15,20-tetraphenylporphyrin, cyclopropa[b]chlorins, or trans-bis(dicyanomethyl)chlorins occurs in the pyrrole subunit opposite the substituted ring; exhaustive bromination of functionalized tetraphenylchlorins provides a route to dodecasubstitued dihydroporphyrins for the first time.

  2-硝基-5,10,15,20-四苯基卟啉、环丙烯[b]氯素或反式-双(氰基甲基)氯素的区域选择性溴化发生在与取代环相对的吡咯亚基上；功能化四苯基氯素的彻底溴化首次提供了通往十二取代二氢卟啉的路线。
• 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。
• Ethyl Acetoacetate and Acetylacetone Appended Hexabromo Porphyrins: Synthesis, Spectral, Electrochemical, and Femtosecond Third-Order Nonlinear Optical Studies
  作者：Renu K Rohal、Dipanjan Banerjee、Tavleen Manchanda、Varusha Bhardwaj、Venugopal Rao Soma、Sankar Muniappan

  DOI：10.1039/d3dt00005b

  日期：——

  β-heptasubstituted porphyrins exhibited keto–enol tautomerism, as supported by 1H NMR spectroscopy. The six bulky bromo and EAA/acac groups made the macrocyclic ring highly electron deficient and nonplanar such that the quantum yield and fluorescence intensity for H2TPP[EAA]Br6 and H2TPP[acac]Br6 were severely reduced in contrast to those values for H2TPP. The poor electron density and nonplanarity over the

  合成了在 β 位具有六个溴原子的乙酰乙酸乙酯或乙酰丙酮（EAA 或 acac）的不对称取代卟啉，然后通过各种光谱技术（例如 UV-Vis、荧光和 NMR）以及 CV、DFT、MALDI-进行表征TOF-MS 和元素分析。机理途径遵循与 MTPP(NO 2 )Br 6 (M = 2H、Cu( II ) 和 Ni( II )) 的亲核取代反应（亲核试剂：EAA 和 acac），生成的 β-七取代卟啉表现出酮-烯醇互变异构，由1支持核磁共振氢谱。六个庞大的溴和 EAA/acac 基团使大环高度缺电子和非平面，使得 H 2 TPP[EAA]Br 6和 H 2 TPP[acac]Br 6的量子产率和荧光强度与H 2 TPP的那些值。卟啉环上较差的电子密度和非平面性使 MTPP[X]Br 6 [M = 2H、Cu( II ) 和 Ni( II); X = EAA 或 acac] 与相应的 MTPP 相