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The encapsulation of functional molecules inside porous coordination polymers (also known as metal-organic frameworks, MOFs) has become of great interest in recent years at the field of multifunctional materials. In this article, we present a study of the effects of size and charge in the anion exchange process of a Gd based MOF, involving molecular species like polyoxometalates (POMs), and [AuCl₄] - . This post-synthetic modification has been characterized by IR, EDAX, and single crystal diffraction, which have provided unequivocal evidence of the location of the anion molecules in the framework.