SCHEDULED MAINTENANCE
Functionalized fluorescent terephthalate monomers and their attempted polyester formation†
Abstract
The reaction of diethyl 2,5-bis(tert-butyl)phenoxy-3,6-dihydroxyterephthalate (1) with tetraethylene glycol di(p-toluenesulfonate) under high-dilution conditions afforded several isolated products. Two products were identified as macrocycles with one being the 1 + 1 crown ether derivative 3 (10% yield), and the second being the 2 + 2 crown ether compound D3 (19% yield). The X-ray structure for 3 was determined with the asymmetric unit observed to comprise half of the molecule. The small crown ether ring of 3 interacts with K+ or H+ ions in MeOH, but binding is weak and the macrocyclic cavity is too small to fully encapsulate the K+ ion. Transesterification of compounds 1, its methylated version 2 and 3 with diols such as ethylene glycol or 1,4-butandiol produced monomers (M1–M3) which were reacted with terephthaloyl chloride. Short oligomers were produced (PolyM1–PolyM3) rather than extensive polymeric materials and all displayed solid state fluorescence. The absorption and fluorescence properties of M1–M2 and their polymers can be related to subtle structural changes. The Stokes shift for M2 of 15 627 cm−1 in DCM is one of the largest observed for a simple organic chromophore in fluid solution.
Please wait while we load your content...
