Abstract
Many luminescent stimuli responsive materials are based on fluorescence emission, while stimuli-responsive room temperature phosphorescent materials are less explored. Here, we show a kind of stimulus-responsive room temperature phosphorescence materials by the covalent linkage of phosphorescent chromophore of arylboronic acid and polymer matrix of poly(vinylalcohol). Attributed to the rigid environment offered from hydrogen bond and B-O covalent bond between arylboronic acid and poly(vinylalcohol), the yielded polymer film exhibits ultralong room temperature phosphorescence with lifetime of 2.43 s and phosphorescence quantum yield of 7.51%. Interestingly, the RTP property of this film is sensitive to the water and heat stimuli, because water could destroy the hydrogen bonds between adjacent poly(vinylalcohol) polymers, then changing the rigidity of this system. Furthermore, by introducing another two fluorescent dyes to this system, the color of afterglow with stimulus response effect could be adjusted from blue to green to orange through triplet-to-singlet Förster-resonance energy-transfer. Finally, due to the water/heat-sensitive, multicolor and completely aqueous processable feature for these three afterglow hybrids, they are successfully applied in multifunctional ink for anti-counterfeit, screen printing and fingerprint record.
Highlights
Many luminescent stimuli responsive materials are based on fluorescence emission, while stimuli-responsive room temperature phosphorescent materials are less explored
Arylboronic acid, 1,1′:3′,1”-terphenyl-5′-boronic acid, which tends to occur dehydration condensation reaction for the existence of boronic acid unit[26], was chosen as a phosphorescent chromophore to react with poly(vinylalcohol) (PVA) polymer chains, to yield DPP-BOH-PVA (Fig. 1)
The hydroxyl groups in PVA could react with the hydroxyl groups of DPP-BOH to form B–O covalent bonds, which could limit the thermal motion of DPP-BOH molecule, facilitating room-temperature phosphorescence (RTP) emission; on the other hand, PVA exhibits excellent hydroscopicity
Summary
Many luminescent stimuli responsive materials are based on fluorescence emission, while stimuli-responsive room temperature phosphorescent materials are less explored. The RTP property of this film is sensitive to the water and heat stimuli, because water could destroy the hydrogen bonds between adjacent poly(vinylalcohol) polymers, changing the rigidity of this system By introducing another two fluorescent dyes to this system, the color of afterglow with stimulus response effect could be adjusted from blue to green to orange through triplet-tosinglet Förster-resonance energy-transfer. The resultant RTP property could be controlled by the alternating stimulation of heat and water By introducing another two fluorescent dyes to this system, such as fluorescein and rhodamine B, the afterglow color could be adjusted through triplet-to-singlet Förster-resonance energy transfer (TS-FRET). All the products in this work are accessible to be obtained, which may provide a new perspective for designing stimulus-responsive ultralong RTP materials
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