Five novel trans-A₂B₂ porphyrins bearing 4-pyridyl groups at 5- and 15-meso-positions (‘A’ substituent) and different functional groups at 10- and 20-meso-positions (‘B’ substituent) have been synthesised [5,15-di(4′-pyridyl)-10,20-di(thienyl) porphyrin (DPyDThP, 1), 5,15-di(4′-pyridyl)-10,20-di(4′-nitrophenyl) porphyrin (DPyDNO₂P, 2), 5,15-di(4′-pyridyl)-10,20-di(phenanthryl) porphyrin (DPyDPhnP, 3), 5,15-di(4′-pyridyl)-10,20-di(pyrenyl) porphyrin (DPyDPyrP, 4) and 5,15-di(4′-pyridyl)-10,20-di(3′,5′-dicarboxy) zinc porphyrin (DPyTcZP, 5)]. The compounds are fully characterised by NMR spectroscopy and mass spectrometry. The absorbance and emission studies of the porphyrins have been conducted, revealing the effect of the substituents at the 10,20-positions on the optical properties of the compounds. The porphyrins (1–5) were further reacted with transition metals (Mn^II, Co^II and Zn^II) under solvothermal conditions that led to the generation of coordination polymers (CPs) 1a–5a [Co-DPyDThP CP (1a), Zn-DPyDThP CP (1b), Co-DPyDNO₂P CP (2a), Mn-DPyDNO₂P CP (2b), Co-DPyDPhnP CP (3a), Zn-DPyDPhnP CP (3b), Co-DPyDPyrP CP (4a), Mn-DPyDPyrP CP (4b), Zn-DPyDPyrP CP (4c), Zn-DPyTcZP CP (5a)]. The CPs were characterized by single crystal X-ray diffraction studies, manifesting the influence of the substituents on their structural patterns. It has been observed that CP 1a adopts a 1D double chain structure while 1b and 2a are isostructural with a 3D framework, containing large hexagonal channels. Under the same reaction conditions as for 2a, CP 2b assumes a 1D-chain structure unlike 2a. Both the CPs 3a and 3b exhibit 2D square-grid type architecture whereas CPs 4a, 4b and 4c represent 1D zigzag polymeric chain structures. CP 5a is rather different, due to the active coordination of both the substituents (4-pyridyl and 3,5-dicarboxyphenyl), and reveal an attractive 2D grid-like architecture containing two kinds of voids.

中文翻译：

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新型的介孔取代的反式-A ₂ B ₂卟啉：其金属介导的超分子组装体的合成与结构

五个新的反式-A ₂ B ₂卟啉在5和15-内消旋位（'A'取代基）和不同的官能团在10和20-内消旋位（'B'取代基）带有卟啉合成的[5,15-二（4'-吡啶基）-10,20-二（噻吩基）卟啉（DPyDThP，1），5,15-二（4'-吡啶基）-10,20-二（4'-硝基苯基）卟啉（DPyDNO ₂ P，2），5,15-二（4'-吡啶基）-10,20-二（菲基）卟啉（DPyDPhnP，3），5,15-二（4'-吡啶基）- 10,20-二（苯基）卟啉（DPyDPyrP，4）和5,15-二（4'-吡啶基）-10,20-二（3'，5'-二羧基）锌卟啉（DPyTcZP，5）]。通过NMR光谱和质谱法充分表征了这些化合物。进行了卟啉的吸收和发射研究，揭示了在10,20位上的取代基对化合物的光学性能的影响。在溶剂热条件下，卟啉（1-5）与过渡金属（Mn ^II，Co ^II和Zn ^II）进一步反应，导致生成配位聚合物（CP）1a-5a [Co-DPyDThP CP（1a），Zn -DPyDThP CP（1b），Co-DPyDNO ₂ P CP（2a），Mn-DPyDNO ₂ P CP（2b），Co-DPyDPhnP CP（2b）3a），Zn-DPyDPhnP CP（3b），Co-DPyDPyrP CP（4a），Mn-DPyDPyrP CP（4b），Zn-DPyDPyrP CP（4c），Zn-DPyTcZP CP（5a）]。CP通过单晶X射线衍射研究表征，表明取代基对其结构模式的影响。已经观察到，CP 1a采用一维双链结构，而1b和2a是具有3D框架的同构结构，包含大的六边形通道。在与2a相同的反应条件下，CP 2b与2a不同，呈现1D链结构。两个CP 3a图3a和3b显示2D正方形网格型结构，而CP 4a，4b和4c代表1D之字形聚合物链结构。由于两个取代基（4-吡啶基和3,5-二羧基苯基）的主动配位，CP 5a相当不同，并显示出包含两种空隙的有吸引力的二维网格状结构。