Jump to main content
Jump to site search

Issue 45, 2017
Previous Article Next Article

Novel meso-substituted trans-A2B2 porphyrins: synthesis and structure of their metal-mediated supramolecular assemblies

Author affiliations

Abstract

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 (MnII, CoII and ZnII) 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.

Graphical abstract: Novel meso-substituted trans-A2B2 porphyrins: synthesis and structure of their metal-mediated supramolecular assemblies

Back to tab navigation

Supplementary files

Publication details

The article was received on 12 Sep 2017, accepted on 28 Oct 2017 and first published on 30 Oct 2017


Article type: Paper
DOI: 10.1039/C7CE01642E
Citation: CrystEngComm, 2017,19, 6845-6857
  •   Request permissions

    Novel meso-substituted trans-A2B2 porphyrins: synthesis and structure of their metal-mediated supramolecular assemblies

    S. Goswami, B. K. Tripuramallu and I. Goldberg, CrystEngComm, 2017, 19, 6845
    DOI: 10.1039/C7CE01642E

Search articles by author

Spotlight

Advertisements