Hybrid materials such as coordination polymers and metal-organic frameworks find application in areas as diverse as gas storage, rad-waste immobilization, micro-electronics and catalysis. Those containing lanthanide (Ln) or actinide (An) compositions (aka the ‘f-elements’) are of particular importance to the nuclear fuel cycle and related environmental issues. Further, Ln elements see application in areas from medical imaging to magnetic materials and sensing devices. Synthetic routes for producing these materials often include soft-chemical or molecular design approaches. Soluble molecular precursors or even dense phase minerals provide the structural building units that are induced to assemble via covalent and non-covalent (e.g. hydrogen- and/or halogen- bonding) interactions. Investigation of the properties of these (and other) types of materials is closely related to an understanding of their crystal structures. As such, a major focus of our group is the X-ray structural characterization of large families of both novel and naturally occurring solid-state compounds to establish assembly criteria and structure-property relationships, with a particular emphasis on luminescence behavior.