The useful concepts
of reticular chemistry, rigid and predictable
metal nodes together with strong and manageable covalent interactions
between metal centers and organic linkers, have made the so-called
metal–organic frameworks (MOFs) a flourishing area of enormous
applicability. In this work, the extension of similar strategies to
supramolecularly assembled metal–organic materials has allowed
us to obtain a family of isoreticular compounds of the general formula
[Cu7(μ-adeninato-κN3:κN9)6(μ3-OH)6(μ-OH2)6](OOC-R-COO)·nH2O (R: ethylene-, acetylene-, naphthalene-, or biphenyl-group) in
which the rigid copper–adeninato entities and the organic dicarboxylate
anions are held together not by covalent interactions but by a robust
and flexible network of synergic hydrogen bonds and π–π
stacking interactions based on well-known supramolecular synthons
(SMOFs). All compounds are isoreticular, highly insoluble, and water-stable
and show a porous crystalline structure with a pcu topology
containing a two-dimensional (2D) network of channels, whose dimensions
and degree of porosity of the supramolecular network are tailored
by the length of the dicarboxylate anion. The partial loss of the
crystallization water molecules upon removal from the mother liquor
produces a shrinkage of the unit cell and porosity, which leads to
a color change of the compounds (from blue to olive green) if complete
dehydration is achieved by means of gentle heating or vacuuming. However,
the supramolecular network of noncovalent interactions is robust and
flexible enough to reverse to the expanded unit cell and color after
exposure to a humid atmosphere. This humidity-driven breathing behavior
has been used to design a sensor in which the electrical resistance
varies reversibly with the degree of humidity, very similar to the
water vapor adsorption isotherm of the SMOF. The in-solution adsorption
properties were explored for the uptake and release of the widely
employed 5-fluorouracil, 4-aminosalycilic acid, 5-aminosalycilic acid,
and allopurinol drugs. In addition, cytotoxicity activity assays were
completed for the pristine and 5-fluorouracil-loaded samples.