Directing the Morphology, Packing, and Properties of Chiral Metal–Organic Frameworks by Cation Exchange. (4th July 2022)

• Record Type: Journal Article
• Authors: Nasi, Hadar; Chiara di Gregorio, Maria; Wen, Qiang; Shimon, Linda J. W.; Kaplan‐Ashiri, Ifat; Bendikov, Tatyana; Leitus, Gregory; Kazes, Miri; Oron, Dan; Lahav, Michal; van der Boom, Milko E.
• Is Part Of: Angewandte Chemie. Volume 134:Number 34(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-07-04
• Subjects: Cathodoluminescence -- Fluorescence -- Magnetic Properties -- Metal Cation Metathesis -- Metal–Organic Frameworks; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202205238
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: We show that metal–organic frameworks, based on tetrahedral pyridyl ligands, can be used as a morphological and structural template to form a series of isostructural crystals having different metal ions and properties. An iterative crystal‐to‐crystal conversion has been demonstrated by consecutive cation exchanges. The primary manganese‐based crystals are characterized by an uncommon space group ( P 622). The packing includes chiral channels that can mediate the cation exchange, as indicated by energy‐dispersive X‐ray spectroscopy on microtome‐sectioned crystals. The observed cation exchange is in excellent agreement with the Irving–Williams series (MnZn) associated with the relative stability of the resulting coordination nodes. Furthermore, we demonstrate how the metal cation controls the optical and magnetic properties. The crystals maintain their morphology, allowing a quantitative comparison of their properties at both the ensemble and single‐crystal level. Abstract : Quantitative exchange of metal cations has resulted in a variety of crystals having different optical and magnetic properties but with retention of the crystal shape. Crystals isolated during the exchange exhibited higher concentrations of the incoming metal cations at the hexagonal basal faces, which suggests that the nanochannels are mediating the process.