ABSTRACT
[This corrects the article DOI: 10.1039/D1RA00129A.].
ABSTRACT
Large (mega) Stokes shift molecules have shown great potential in white light emission for optoelectronic applications, such as flat panel display technology, light-emitting diodes, photosensitizers, molecular probes, cellular and bioimaging, and other applications. This review aims to summarize recent developments of white light generation that incorporate a large Stokes shift component, key approaches to designing large Stokes shift molecules, perspectives on future opportunities, and remaining challenges confronting this emerging research field. After a brief introduction of feasible pathways in generating white light, exemplifications of large Stokes shift molecules as white light candidates from organic and inorganic-based materials are illustrated. Various possible ways to design such molecules have been revealed by integrating the photophysical mechanisms that are essential to produce red-shifted emission upon photoexcitation, such as excited state intramolecular proton transfer (ESIPT), intramolecular charge transfer (ICT), excited state geometrical relaxation or structural deformation, aggregation-induced emission (AIE) alongside the different formations of aggregates, interplay between monomer and excimer emission, host-guest interaction, and lastly metal to ligand charge transfer (MLCT) via harvesting triplet state. Furthermore, previously reported fluorescent materials are described and categorized based on luminescence behaviors on account of the Stokes shifts value. This review will serve as a rationalized introduction and reference for researchers who are interested in exploring large or mega Stokes shift molecules, and will motivate new strategies along with instigation of persistent efforts in this prominent subject area with great avenues.
ABSTRACT
Various reports demonstrated that azobenzene derivatives are the chromophore of choice in photoresponsive surfaces showing reversible surface polarity. Hitherto the surface study of coating films based on polymer/azobenzene blends using contact angle measurements remained unexplored. To provide insight into the surface polarity of polymer/dye blend films, poly(methyl methacrylate) (PMMA) blends containing photoresponsive 4-hydroxy-4'-methylazobenzene (AZO1) and 4,4'-dimethylazobenzene (AZO2) as coating films on clear glass substrates are investigated in this work. Contact angle measurements were carried out to unravel the role of substituents in the surface polarity and the orientation of chromophores in the coating matrices before and after UV light (λ max = 365 nm) irradiation. Changes in water contact angles measured on the PMMA/azobenzene coating films indicated that the surface polarity is reversible as the chromophores underwent reversible trans-cis isomerisation. It has been revealed that the repeated trans-cis isomerisation led to the random reorientation and arrangement of chromophores in PMMA/AZO1 coating films. Then, to indicate the possibility of the disruption of interfacial interactions due to the repeated trans-cis isomerisation processes, as a proof of concept experiment, it is shown that the commercial acrylic-based pressure-sensitive sticker which adhered strongly to the PMMA/AZO1(13) coating film is peeled off from the coating surface after being subjected to a cycle of UV light irradiation for 12 hours, followed by dark conditions for another 12 hours within 14 days. The proof of concept study will lead to more development of smart photoresponsive coating films using simple polymer/dye blends.
