Engineering of porous π-stacked solids using mechanochemistry

Abstract

Charge-assisted p-stacking interactions result in the formation of large porous arrays formed from the inclusion of metal tris(phenanthroline) cations into p-sulfonatocalix-[4]arene anions.

Organometallic chemistry in the melt phase

“…The successful engineering of extended p-stacked arrays based on charge assisted interactions between psulfonatocalix [4]arene anions and 1,10-phenanthroline Ni cations has been reported by Nichols et al [42]. The compound was obtained from the grinding of Ni(NO 3 ) 2 AE 6H 2 O with 1,10-phenanthroline followed by grinding with the p-sulfonatocalix [4]arene penta-anion.…”

Supramolecular Assemblies of Sulfonatocalixarenes with Phenanthroline: Factors Governing Capsule Formation versus Bilayer Arrangements

“…Phen was selected as a suitable guest because the inclusion complexation of Phen within CAS molecules is likely to result in the formation of a p-stacked motif, and offers the possibility of building novel aggregations. [16] A total of five solid-state complexes were synthesized: capsule complexes 1-3 are formed at pH 1-2, whereas the remaining complexes (4 and 5) are formed by the disassembly of the capsules that occurs in a more acidic mother liquor of 1 m HCl. Furthermore, a host-guest solution study was performed by using NMR spectroscopy for comparison with previous results.…”

Photophysical and electrochemical properties of the outer-sphere associate of [Ru(bipy)3]2+ with p-sulfonatothiacalix[4]arene

“…10 For in stance, an analysis of the supramolecular structure of an inclusion complex of [Ni(phen) 3 ] 2+ with p sulfonato calix [4]arene revealed a chain of π stacked [Ni(phen) 3 ] 2+ cations. 10 According to X ray diffraction data for an out er sphere associate with [Ru(bipy) 3 ] 2+ , the arrangement of the [Ru(bipy) 3 ] 2+ cations is favorable for π stacking. However, the shortest distance between the centers of the aromatic rings (3.89 Å) is longer by 0.3 Å than the sum of the corresponding van der Waals radii.…”

“…5-9 Water soluble calixarenes, es pecially their sulfonate derivatives, constitute a novel class of macrocyclic compounds under intensive development, which can be regarded as a new type of outer sphere ligands for charged coordinatively saturated transition metal com plexes. [10][11][12][13][14][15][16] For instance, the study 16,17 of the influence of outer sphere association of p sulfonatocalix [4(8)]arenes with [Ru(bipy) 3 ] 2+ on the photophysical properties of the metal complex revealed an increased emission intensity of [Ru(bipy) 3 ] 2+ in the case of p sulfonatocalix [8]arene 16 and emission quenching in the case of p sulfonatocalix [4] arene. 17 The causes behind such different effects still re main unclear.…”