Embodiments described herein relate to compns. including iptycene-based structures and extended iptycene structures. The iptycene-based compd. comprises an iptycene core and at least one optionally substituted heterocyclyl or optionally substituted heteroaryl moiety rigidly bonded to the iptycene core, wherein the optionally substituted heterocyclyl or optionally substituted heteroaryl moiety defines at least a portion of the iptycene core. In some embodiments, the compns. may be useful in org. light-emitting diodes (OLEDs), org. photovoltaics, and other devices. [on SciFinder(R)]