Cluster-Expanded Solids: A Strategy for Assembling Functional Porous Materials

Abstract

This grant provided (partial) support for the research efforts of three graduate students and two undergraduate students. The intention of the program was to explore the use of molecular precursors in generating functional porous materials with precisely tailored structures and properties. Prior work in our laboratory had demonstrated the feasibility of employing face-capped octahedral clusters of the type [Re 6 Q 8 (CN) 6 ] 3-/4- (Q = S, Se, Te) in the expansion of known metal-cyanide frameworks. For example, the use of [Re 6 Se 8 (CN) 6 ] 4- as a reactant in place of [Fe(CN) 6 ] 4- resulted in formation of Fe 4 [Re 6 Se 8 (CN) 6 ] 3 ·36H 2 O, featuring an expanded form of the porous three-dimensional framework of Prussian blue (Fe 4 [Fe(CN) 6 ] 3 ·14H 2 O). This compound could be dehydrated without loss of integrity, and the increase in void volume significantly enhances its capacity as a molecular sieve, enabling absorption of larger molecules. For this project, we continued with our efforts to devise new routes to microporous coordination solids that function as molecular sieves, sensors, or catalysts. In particular, our focus was on: (i) the synthesis of new molecular precursors of specific utility for such purposes, and (ii) attempts to incorporate these and existing molecular precursors into new coordination solids. Investigations of the terminal ligand substitution chemistry of the carbon-centered, trigonal prismatic cluster [W 6 CCl 18 ] 2- generated the solvated species [W 6 CCl 12 (DMF) 6 ] 2+ and [W 6 CCl 12 (py) 6 ] 2+ , as well as the potential framework building units [W 6 C(CN) 18 ] 3- , [W 6 CCl 12 (pyrazine) 6 ] 2+ , [W 6 CCl 12 (4-cyanopyridine) 6 ] 2+ , and [W 6 CCl 12 (4,4'-bipyridine) 6 ] 2+ . Efforts to produce microporous magnets capable of performing magnetic separations led to characterization of the microporous Prussian blue analogues CsNi[Cr(CN) 6 ] and Cr 3 [Cr(CN) 6 ] 2 ·6H 2 O. With BET surface areas of 370 m 2 /g and 390 m 2 /g, respectively, these compounds exhibit show ferrimagnetic ordering at temperatures of 65 and 220 K, respectively, the highest ordering temperatures yet observed for any microporous magnet. Efforts to produce actinide-based cluster building units were also undertaken, as were experiments probing the reactivity of new metal-organic frameworks possessing coordinatively-unsaturated metal centers. This research further provided an excellent opportunity for training graduate and undergraduate students in the synthesis and characterization of inorganic materials.