A Thermally Stable Pt/Y-Based Metal−Organic Framework: Exploring the Accessibility of the Metal Centers with Spectroscopic Methods Using H2O, CH3OH, and CH3CN as Probes

Abstract

A metal−organic framework (MOF) based on Pt, Y, and 2,2‘-bipyridine-5,5‘-dicarboxylate (BPDC), stable up to 400 °C, has been synthesized and characterized. In this MOF, the Pt centers are coordinated to Cl and the N atoms of the BPDC unit, giving a local environment similar to that found in a series of Pt−organic complexes with catalytic activity toward C−H bond cleavage of alkanes. This new material is a heterogeneous counterpart to the corresponding metal−organic complex. The structure, determined by single-crystal XRD data, is the repetition of three covalently bonded layers. These layers form a block, which is stacking as an (a)(b)(c) sequence along the crystallographic b-axis. Each layer contains the Pt−organic unit, while Y atoms represent the connection between adjacent layers. No covalent connection is present between layer (a) of a block and layer (c) of an adjacent block. EXAFS (BM29 at the ESRF) analysis supports the XRD data. As this MOF crystallizes under hydrothermal conditions, water acts both as solvent and as a direct ligand of Y. Accessibility to the metal centers is demonstrated by reversible water desorption/readsorption, as determined by TPA/TPD, FTIR, UV−vis, EXAFS, and XANES. Importantly, the results show that the as-synthesized material will not suffer a permanent loss in porosity upon solvent removal. In addition to water, methanol, ethanol, and acetonitrile can also access the internal void of the dehydrated phase.