Anion Coordination in Metal−Organic Frameworks Functionalized with Urea Hydrogen-Bonding Groups

A series of metal−organic frameworks (MOFs) functionalized with urea hydrogen-bonding groups has been synthesized
and structurally analyzed by single-crystal X-ray diffraction to evaluate the efficacy of anion coordination by urea within the structural
constraints of the MOFs. We found that urea-based functionalities may be used for anion binding within metal−organic frameworks
when the tendency for urea···urea self-association is decreased by strengthening the intramolecular CH···O hydrogen bonding of
N-phenyl substituents to the carbonyl oxygen atom. Theoretical calculations indicate that N,N‘-bis(m-pyridyl)urea (BPU) and N,N‘-bis(m-cyanophenyl)urea (BCPU) should have enhanced hydrogen-bonding donor abilities toward anions and decreased tendencies
to self-associate into hydrogen-bonded tapes compared to other disubstituted ureas. Accordingly, BPU and BCPU were incorporated
in MOFs as linkers through coordination of various Zn, Cu, and Ag transition metal salts, including Zn(ClO4)2, ZnSO4, Cu(NO3)2,
Cu(CF3SO3)2, AgNO3, and AgSO3CH3. Structural analysis by single-crystal X-ray diffraction showed that these linkers are versatile
anion binders, capable of chelate hydrogen bonding to all of the oxoanions explored. Anion coordination by the urea functionalities
was found to successfully compete with urea self-association in all cases except for that of charge-diffuse perchlorate.