Exclusive Hydrophobic Self-Assembly of Adaptive Solid-State Networks of Octasubstituted 9,9′-Spirobifluorenes

An easy and powerful access to 3,3′,6,6′-tetrasubstituted 9,9′-spirobifluorene derivatives with tetrahedral orientation of the peripheral groups (i.e., −I, −CN, −NO2, −CHO, −COOH, −CCH, −4-Py) was developed. The NMR and HRMS results are in agreement with the proposed formula and the solid-state molecular structures obtained by single-crystal X-ray diffraction. They form molecular solids self-assembled via exclusive hydrophobic interactions. Solid-state selection and adaptation can be obtained on the basis of variable compact packing of functional groups present on the 9,9′-spirobifluorene backbone.