Predictably Ordered Open Hydrogen-Bonded Networks Built from Indeno[1,2-b]fluorenes

Predictably ordered materials can be constructed by a modular strategy in which properly designed molecular components are positioned in space by reliable interactions. In principle, this approach can be used to control the arrangement of adjacent systems of pi-conjugation, thereby creating molecular materials with valuable optoelectronic properties. To explore this possibility, we have synthesized compounds in which 2,4-diamino-1,3,5-triazinyl groups are attached to derivatives of 6,12-dihydroindeno[1,2-b]fluorene to produce molecules with well-defined cruciform topologies, extended pi-conjugated aromatic cores, and an ability to form multiple hydrogen bonds. These compounds crystallize to form robust open hydrogen bonded networks with parallel indenofluorenyl cores, significant volume (64-70%) available for accommodating guests, and characteristic luminescence. Our results will help permit the rational design of complex new molecular materials in which multiple optoelectronically active components are arranged in productive ways.