Experiments are described that introduce students to the important concepts of host−guest chemistry and size exclusion in porous metal−organic frameworks (MOFs). The experiment has been successfully carried out in both introductory and advanced-level inorganic chemistry laboratories. Students synthesized the porous MOF, α-Mg 3 (O 2 CH) 6 , and examined its ability to take up a variety of small organic molecules into its pores using 1 H NMR spectroscopy. The MOF exhibited size exclusion and students rationalized this behavior based on the structures of the organic molecules and the pore size of the MOF. R esearch into the design and synthesis of extended materials with specific properties has received extensive interest in recent times. Of the many classes of extended materials, metal−organic frameworks (MOFs) have received tremendous attention. MOFs are hybrid materials, composed of metal ions and organic molecules that are linked into an extended array by what is often referred to as a node-and-linker approach. The most successful synthesis of these materials uses metal−carboxylate systems. 1 In many cases, metal carboxylates form frameworks that enclatherate solvent molecules. In some instances, these materials are robust to solvent removal, generating a porous framework. The porous nature of many MOFs makes them attractive for numerous applications involving the uptake and exchange of small molecules. 2 MOFs are ideal for such purposes as the size and shape of the pores may be controlled through judicious choice of metal ions and organic linker molecules.Despite the high level of interest in MOF materials in the academic setting, undergraduate students rarely receive exposure to such cutting-edge applications of inorganic chemistry. Recently, Sumida and Arnold published a MOF laboratory designed for the undergraduate inorganic chemistry laboratory that gives students excellent examples of synthesis and characterization of such materials. 3 The laboratory experiment described herein provides an 1 H NMR-based study of the uptake properties of the MOF α-magnesium formate, α-Mg 3 (O 2 CH) 6 . 4 While students will gain experience in the synthesis of MOF materials, the novelty of this experiment focuses on the host−guest chemistry of porous materials. Host−guest studies have been the topic of a variety of contributions to this Journal, yet none have focused specifically on such properties in MOFs. 5 As many institutions do not have direct access to some of the instrumentation common to MOF characterization, such as X-ray diffraction and gas sorption equipment, this system uniquely provides a straightforward investigation of small molecule uptake and size selectivity of the MOF using NMR spectroscopy. Guest uptake by the MOF can be determined by dissolving the material in D 2 O and obtaining a 1 H NMR spectrum.