Porous molecular crystals derived from cofacial porphyrin/phthalocyanine heterodimers.

26 March 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Porphyrin-based porous materials are of growing interest as heterogeneous catalysts especially for reactions that are of importance to sustainability. Here we demonstrate that porous molecular crystals can be prepared by the simple co-crystallisation of tetraphenylporphyrin (TPP) with octa(2’,6’-di-iso-propylphenoxy)phthalocyanine and its metal complexes [(dipPhO)8PcM; M = H2, Al-OH, Ti=O, Mn-Cl, Fe-Cl, Co, Ni, Cu, Zn, Ga-Cl, Ag, In-Cl or Au-Cl]. This process is facilitated by the efficient formation of the supramolecular heterodimer between TPP and (dipPhO)8PcM, which is driven by the complementary symmetry and shape of the two macrocycles. The (dipPhO)8PcM component direct the crystal structure to form Phthalocyanine Nanoporous Crystals (PNCs) of similar structure to those formed by (dipPhO)8PcM alone. The incorporation of TPP appears to partially stabilise the PNCs towards the removal of included solvent and for cocrystals containing (dipPhO)8PcCo stability can be enhanced further by the in-situ addition of 4,4-bipyridyl to act as a “molecular wall tie”. These stabilised PNC/TPP cocrystals have a Brunauer-Emmett-Teller surface area (SABET) of 454 m2 g-1 and a micropore volume (Vmp) of 0.22 ml g-1. The reactivity of both macrocycles within the PNC/TPP co-crystals are demonstrated by in-situ metal insertion.

Keywords

porous materials
porphyrins
phthalocyanine

Supplementary materials

Title
Description
Actions
Title
Supplemental information
Description
A .res file of the low resolution scXRD data for is included in the ESI along with details of the synthesis of (dipPhO)8PcFe-N-FeTPP, general procedure for crystallisations and spectra from the 1H NMR titration.
Actions
Title
structure of (dipPhO)8PcFe-N-FeTPP as .res file
Description
low resolution scXRD structure of (dipPhO)8PcFe-N-FeTPP as .res file
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.