Cholesteric mesophase based 1D photonic materials from self-assembly of liquid crystalline block and random terpolymers containing chromonic molecules

We describe the influence of competing self-organizing phenomena on the formation of cholesteric mesophase in liquid crystalline brush block terpolymers (LCBBTs) and liquid crystalline random brush terpolymers (LCRBTs) containing chromonic molecules. A library of LCBBTs and LCRBTs are synthesized using ring-opening metathesis polymerization (ROMP) of norbornene side-chain functionalized monomers comprising cholesteryl mesogen (NBCh9), chromonic xanthenone (NBXan), and poly(ethylene glycol) (NBMPEG). Compression molded films of LCRBTs containing chromonic molecules display multilevel hierarchical structure in which cholesteric mesophase co-exists with π–π stacking of the chromonic mesophase along with PEG microphase segregated domains. This is unexpected as conventional LCBCPs and LCBBCs that lack chromonic molecules do not form cholesteric mesophases. The presence of π–π interactions modifies the interface at the IMDS so that both chromonic and cholesteric mesophases coexist leading to the manifestation of cholesteric phase for the first time within block architecture and is very reminiscent of previously published LCRBCs without chromonic molecules. The key to the observed hierarchical assembly in these LCBBTs containing chromonic molecules lies in the interplay of LC order, chromonic π–π stacking, PEG side chain microphase segregation, and their supramolecular cooperative motion. This unique “single component” polymer scaffold transforms our capacity to attain nanoscale hierarchies and optical properties from block architecture similar to nanoscale mesophases resulting in random architecture.