Issue 33, 2017

Solid-state inclusion of C60 and C70 in a co-polymer induced by metal–ligand coordination of a Zn–porphyrin cage with a bis-pyridyl perylene derivative

Abstract

We describe three unprecedented solid-state crystal structures (1–3) involving two (1) or three (2 & 3) different components: a suitable bis-porphyrin cage, a bis-pyridyl perylene derivative that is too large to bind the cage in a ditopic manner and, for 2 and 3, a fullerene (C60 and C70, respectively). Single co-crystals of the two/three components, suitable for X-ray diffraction analyses, grew from their equimolar mixture in p-xylene solution. Remarkably, the co-polymeric 1D chains that are self-assembled in the solid state possess a metal–organic framework (MOF). The fullerene, C60 (2) or C70 (3), is included in all repeating monomeric units of the Zn(II)–bisporphyrin component, which functions as a molecular cage. The formed 1 : 1 inclusion complexes exhibit a parallel arrangement of the two porphyrin units. In turn, adjacent 1 : 1 inclusion complexes are connected through bis-pyridyl perylene ligands acting as pillars. The exo-axial coordination of Zn-centers with the nitrogen atoms of the pyridyl residues defines a new motif of perylene derivatives sandwiched between the 1 : 1 inclusion complexes. The included fullerenes C60/C70 interact with the porphyrin walls of the cages and their aliphatic spacer chains. In particular, the interactions of Zn(II)–bisporphyrin⋯C60/C70 observed in the 1 : 1 inclusion complexes were analysed using Density Functional Theory (DFT) calculations (PB86-D3/def2-TZVP level of theory) and Molecular Electrostatic Potential (MEP) surfaces, and characterized by means of Bader's theory of “atoms-in-molecules” (AIM). The computation of the energetic features of the diverse noncovalent interactions including Zn–porphyrin⋯π(fullerene) and C–H⋯π(fullerene) interactions revealed their conspicuous role in the stabilization of the one-dimensional supramolecular frameworks for both solid-state crystal structures.

Graphical abstract: Solid-state inclusion of C60 and C70 in a co-polymer induced by metal–ligand coordination of a Zn–porphyrin cage with a bis-pyridyl perylene derivative

Supplementary files

Article information

Article type
Paper
Submitted
08 Nov. 2016
Accepted
13 Dec. 2016
First published
13 Dec. 2016

CrystEngComm, 2017,19, 4911-4919

Solid-state inclusion of C60 and C70 in a co-polymer induced by metal–ligand coordination of a Zn–porphyrin cage with a bis-pyridyl perylene derivative

E. C. Escudero-Adán, A. Bauzá, L. P. Hernández-Eguía, F. Würthner, P. Ballester and A. Frontera, CrystEngComm, 2017, 19, 4911 DOI: 10.1039/C6CE02341J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements