Porous Shape-Persistent Organic Cage Compounds of Different Size, Geometry, and Function.

Abstract

The interest in shape-persistent organic cages is nearly as old as the interest in supramolecular chemistry. In the beginning, organic cages have often been synthesized in a stepwise manner, which is not only laborious but very often also accompanied by low overall yields. In 1988, MacDowell published the one pot high-yielding synthesis of [2 + 3] imine cages based on TREN and aromatic dialdehydes, exploiting the reversible condensation of amines and aldehydes to imines, which was later used by others to make even larger cages on the basis of resorcinarenes. In 2008, the synthesis and characterization of an adamantoid [4 + 6] imine cage by condensation of a C3 v-symmetric triaminotriptycene and commercially available 4- tert-butyl salicyldialdehyde was introduced by the author, which was the ignition of our group activities in this research area. In 2011, we published the first gas-sorption data for this [4 + 6] imine cage: with a measured specific surface area of SABET = 1377 m2/g according to the model of Brunauer-Emmett-Teller (BET) this was twice as high as for the reported smaller cages of Cooper. For a second desolvated polymorph of the same cage, an even higher SABET = 2071 m2/g was determined; still one of the highest surface areas until date for porous organic molecular materials. Subsequently, the influence of the substituent in 4-position of the salicyldialdehyde for the reaction to [4 + 6] imine cages was investigated as well as the role of the phenolic hydroxyl group. It turned out that the phenolic hydroxyl group is crucial as directing group to increase the formation of the cage as well as stabilize the structure by cyclic six-membered intramolecular hydrogen bonds. The concept was extended to other imine-based cages of different geometry and size. For instance, a [4 + 4] cubic structure from triptycene trissalicylaldehyde and triptycene triamine was accessible as an amorphous insoluble solid, able to adsorb 18.2 wt % CO2 at ambient conditions. To gain further insight into the structural needs of the molecular precursors, rigidity and preorientation of reacting sites were investigated on prismatic [2 + 3] and truncated tetrahedral [4 + 4] imine cages, showing that rigidity and preorientation is beneficial or even crucial for cage formation. Furthermore, chiral self-sorting was studied on the basic of racemic triamines. Besides imine condensation, we explored the reversible formation of boronic esters from boronic acids and diols. Triptycene tetraol with its 120° angle between the aromatic units has been used in the condensation with benzene triboronic acid to achieve a large cuboctahedral [12 + 8] cage with pore dimensions of 2 nm, which are by IUPAC definition mesoporous. After activation the measured specific surface area was SABET = 3758 m2/g, a number rarely achieved even for other porous compounds such as threedimensional framework materials. Smaller tetrahedral [4 + 6] boronic ester cages were synthesized too. These cages show a selective gas sorption with preference of saturated hydrocarbon ethane over ethylene and acetylene. What distinguishes porous materials derived from molecular cages from three-dimensional frameworks or networks the most is their solubility; thus, the cages are soluble porous units (SPUs) in a broader sense. Taking advantage of this, [4 + 6] imine cages were postfunctionalized in solution to change the gas sorption properties in the crystalline state. Furthermore, cage solutions were spray-coated onto quartz crystal microbalances to enhance affinity and selectivity for sensing of airborne analytes. In this Account, the contributions from our lab on porous organic cages are presented.