Structural Constraints in the Design of Silver Sulfonate Coordination Networks: Three New Polysulfonate Open Frameworks

Three new silver sulfonate metal−organic frameworks are presented along with a design strategy for future
generations. {[Ag6(mesitylenetrisulfonate)2(H2O)5]·2H2O}∞ (1), {Ag4(durenetetrasulfonate)(H2O)2}∞ (2), and {[Ag4(1,3,5,7-tetrakis(4,4‘-sulfophenyl)adamantane)(H2O)2]·1.3H2O}∞ (3) represent a series of open-framework silver
sulfonate solids where the organic linker plays a key role in determining the overall structure. Compound 1 forms
a pillared layered structure, while compounds 2 and 3 form 3-D nets derived from cross-linking of 1-D columns of
silver sulfonates. All three solids incorporate water molecules, which can be removed to yield a solid stable to in
excess of 300 °C. Powder X-ray diffraction studies and vapor sorption experiments show, for 1 and 2, that the
solids retain their structure when guests are removed and, for all three, that water vapor is resorbed stoichiometrically
by the solids. An idealized silver sulfonate framework is proposed, and upon comparison to the reported structures,
guidelines are proposed for structural constraints in the design of future generations of 1-D and possibly 0-D
aggregate structures.