Polysaccharide Matrix-Induced Room-Temperature Phosphorescence of Organic Small Molecules

doi:10.6023/A23030081

Abstract

Organic materials capable of room-temperature phosphorescence have attracted much attention due to their potentials in the fields of optoelectronics, sensing and imaging. The development of environmentally friendly matrices for inducing room-temperature phosphorescence can provide feasible and sustainable ways for the applications. The present study was designed to achieve matrix-induced room-temperature phosphorescence using polysaccharides as dispersive substrates for organic small molecules. 1-Naphthoic acid (NA) and 4,4'-biphenol (BP) were used as the chromophore to generate phosphorescence. NA and BP were doped in sodium carboxymethyl cellulose (CMC-Na), hyaluronic acid (HA) and chitosan, respectively. Room-temperature phosphorescence from NA and BP was observed in those doped polysaccharide films at ambient condition. The phosphorescence quantum yield of NA in the three polysaccharides was estimated to be about 0.03 and the average phosphorescence lifetime of NA in CMC-Na was estimated to be around 600 ms. The average phosphorescence lifetime of NA in HA and chitosan was estimated to be around 650 and 320 ms, respectively. The phosphorescence quantum yield decreased at high doping contents due to intermolecular quenching that may result from excimer formation and triplet- triplet annihilation of NA. BP in CMC-Na presented a phosphorescence quantum yield of about 0.05, which did not decrease with the increase of doping concentration, and the phosphorescence lifetime was about 1000 ms. The phosphorescence quantum yield of BP in HA and chitosan is about 0.03 and 0.006, respectively. The average phosphorescence lifetime of BP in HA and chitosan was estimated to be around 740 and 210 ms, respectively. Infrared spectroscopic studies showed that the polysaccharide substrates formed hydrogen bonds with NA and BP chromophores. The combination of hydrogen bond formation between the matrix and the emissive molecules, the rigid environment of the matrix and the protection of the chromphore from ambient oxygen led to the observation of phosphorescence of organic molecules at room-temperature. NA- and BP-doped CMC-Na solutions can be used to prepare room-temperature phosphorescence patterns by inkjet printing, enabling phosphorescence information encryption. This study can provide a new feasible way for the development of environmentally friendly room-temperature phosphorescence materials.

Key words: room-temperature phosphorescence, polysaccharide, organic small molecules, energymatrix-induced phosphorescencetransfer

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Yeqin Chen, Jinping Chen, Tianjun Yu, Yi Zeng, Yi Li. Polysaccharide Matrix-Induced Room-Temperature Phosphorescence of Organic Small Molecules[J]. Acta Chimica Sinica, 2023, 81(5): 450-455.

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Fig. & Tab. 7

Figure 1. Structures of organic chromophores and polysaccharide substrates

Figure 2. (a) absorption and fluorescence spectra of NA and BP in methanol (3×10-5 mol/L); fluorescence spectra of NA (b) and BP (c) of different concentrations in methanol; (d) emission spectra of NA and BP in ethanol/methanol (1∶9, V/V) at 77 K (λNAex=300 nm, λBPex=260 nm)

Figure 3. (a) Absorption and emission spectra of CMC-Na/NA film (w=1.9%); (b) emission spectra of CMC-Na/NA films at different doping concentrations in air (λex=300 nm)

NA (w/%)	Φ	Φ_P	τ_av/ms
0.05	—	—	613
0.1	—	—	621
0.2	0.04	0.03	609
1.9	0.06	0.03	575
4.8	0.10	0.02	544
7.4	0.10	0.008	49

Table 1. Emission quantum yields (Φ), phosphorescence quantum yields (Φp), and average phosphorescence lifetime (τav) of CMC-Na/NA films

HA/NA			Chitosan/NA
NA (w/%)	Φ	Φ_P	NA (w/%)	Φ	Φ_P
0.05	—	—	0.05	—	—
0.1	0.05	0.03	0.1	0.04	0.02
0.2	0.05	0.03	0.5	0.04	0.03
0.5	0.04	0.02	1.0	0.03	0.02
1.9	0.09	0.02	1.9	0.02	0.01
4.8	0.08	0.01	4.8	0.01	0.003
7.4	0.10	0.003	7.4	0.01	0.001

Table 2. Emission quantum yields (Φ) and phosphorescence quantum yields (Φp) of HA/NA and Chitosan/NA films

Figure 4. FTIR spectra of CMC-Na, HA and Chitosan films, neat and doping with NA (w=0.5%), respectively

Figure 5. (a), (b) The phosphorescence photos of sun god bird patterns printed with the CMC-Na/NA or CMC-Na/BP inks (w=1.9%) after switching off a 254 nm hand-held UV lamp. (c) The persistent phosphorescence of a TIPC logo printed with CMC-Na/BP ink (excited by a 254 nm UV lamp)

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