Confinement of Atomically Defined Metal Halide Sheets in a Metal-Organic Framework

Abstract

The size-dependent and shape-dependent characteristics that distinguish nanoscale materials from bulk solids arise from constraining the dimensionality of an inorganic structure. As a consequence, many studies have focused on rationally shaping these materials to influence and enhance their optical, electronic, magnetic and catalytic properties. Although a select number of stable clusters can typically be synthesized within the nanoscale regime for a specific composition, isolating clusters of a predetermined size and shape remains a challenge, especially for those derived from two-dimensional materials. Here we realize a multidentate coordination environment in a metal-organic framework to stabilize discrete inorganic clusters within a porous crystalline support. We show confined growth of atomically defined nickel(II) bromide, nickel(II) chloride, cobalt(II) chloride and iron(II) chloride sheets through the peripheral coordination of six chelating bipyridine linkers. Notably, confinement within the framework defines the structure and composition of these sheets and facilitates their precise characterization by crystallography. Each metal(II) halide sheet represents a fragment excised from a single layer of the bulk solid structure, and structures obtained at different precursor loadings enable observation of successive stages of sheet assembly. Finally, the isolated sheets exhibit magnetic behaviours distinct from those of the bulk metal halides, including the isolation of ferromagnetically coupled large-spin ground states through the elimination of long-range, interplay magnetic ordering. Overall, these results demonstrate that the pore environment of a metal-organic framework can be designed to afford precise control over the size, structure and spatial arrangement of inorganic clusters.

Department(s)

Chemistry

Research Center/Lab(s)

Center for High Performance Computing Research

Comments

This research was supported through a Multidisciplinary University Research Initiatives Program funded by the US Department of Defense, Office of Naval Research under award N00014-15-1-2681.

International Standard Serial Number (ISSN)

1476-4687

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2019 The Authors, All rights reserved.

Publication Date

01 Nov 2019

PubMed ID

31739311

Link to Full Text

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