Thermodynamics and Electronic Properties of Heterometallic Multinuclear Actinide-Containing Metal–Organic Frameworks with “Structural Memory” Otega A. Ejegbavwo Corey R. Martin Oyindamola A. Olorunfemi Gabrielle A. Leith Richard T. Ly Allison M. Rice Ekaterina A. Dolgopolova Mark D. Smith Stavros G. Karakalos Nancy Birkner Brian A. Powell Shubham Pandey Robert J. Koch Scott T. Misture Hans-Conrad zur Loye Simon R. Phillpot Kyle S. Brinkman Natalia B. Shustova 10.1021/jacs.9b04737.s010 https://acs.figshare.com/articles/dataset/Thermodynamics_and_Electronic_Properties_of_Heterometallic_Multinuclear_Actinide-Containing_Metal_Organic_Frameworks_with_Structural_Memory_/8793128 Thermodynamic studies of actinide-containing metal–organic frameworks (An-MOFs), reported herein for the first time, are a step toward addressing challenges related to effective nuclear waste administration. In addition to An-MOF thermochemistry, enthalpies of formation were determined for the organic linkers, 2,2′-dimethylbiphenyl-4,4′-dicarboxylic acid (H<sub>2</sub>Me<sub>2</sub>BPDC) and biphenyl-4,4′-dicarboxylic acid (H<sub>2</sub>BPDC), which are commonly used building blocks for MOF preparation. The electronic structure of the first example of An-MOF with mixed-metal AnAn′-nodes was influenced through coordination of transition metals as shown by the density of states near the Fermi edge, changes in the Tauc plot, conductivity measurements, and theoretical calculations. The “structural memory” effect (i.e., solvent-directed crystalline–amorphous–crystalline structural dynamism) was demonstrated as a function of node coordination degree, which is the number of organic linkers per metal node. Remarkable three-month water stability was reported for Th-containing frameworks herein, and the mechanism is also considered for improvement of the behavior of a U-based framework in water. Mechanistic aspects of capping linker installation were highlighted through crystallographic characterization of the intermediate, and theoretical calculations of free energies of formation (Δ<i>G</i><sub><i>f</i></sub>) for U- and Th-MOFs with 10- and 12-coordinated secondary building units (SBUs) were performed to elucidate experimentally observed transformations during the installation processes. Overall, these results are the first thermochemical, electronic, and mechanistic insights for a relatively young class of actinide-containing frameworks. 2019-06-20 00:00:00 MOF preparation Mechanistic aspects building blocks node coordination degree Fermi edge conductivity measurements SBU installation processes metal node acid U-based framework Thermodynamic linker installation formation H 2 Electronic Properties building units transition metals water stability waste administration 2 BPDC Tauc plot calculation actinide-containing frameworks Th-containing frameworks An-MOF thermochemistry