多糖基质诱导有机小分子室温磷光研究

doi:10.6023/A23030081

摘要/Abstract

有机室温磷光材料在光电、传感和成像等领域具有重要的应用前景并受到广泛关注, 发展环境友好的基质用于诱导室温磷光能为室温磷光材料的应用提供更多可行策略. 本研究设计利用多糖作为基质诱导有机小分子产生室温磷光. 研究发现1-萘甲酸(NA)在羧甲基纤维素钠、透明质酸钠和壳聚糖基质中均有室温磷光现象, 室温磷光量子产率约0.03, 在三种多糖基质中的磷光寿命分别为600, 650和320 ms. NA在高掺杂量时易形成激基缔合物以及发生三重态-三重态湮灭, 导致磷光量子产率明显下降. 4,4'-联苯二酚(BP)在三种多糖基质中没有形成激基缔合物, 其中BP在羧甲基纤维素钠中的磷光量子产率约为0.05, 并不随掺杂浓度的增加而降低, 磷光寿命约1000 ms. 红外光谱研究表明多糖基质与NA和BP发色团形成了氢键. 多糖基质与发光分子间的氢键作用、基质的刚性环境以及对环境氧气的隔离三者共同作用, 使有机小分子产生室温磷光. NA和BP掺杂的羧甲基纤维素钠溶液可以通过喷墨打印制备室温磷光图案.

关键词: 室温磷光, 多糖, 有机小分子, 基质诱导室温磷光

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

引用此文

谌业勤, 陈金平, 于天君, 曾毅, 李嫕. 多糖基质诱导有机小分子室温磷光研究[J]. 化学学报, 2023, 81(5): 450-455.

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

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图/表 7

图1. 有机发光小分子和多糖基质的化学结构

Figure 1. Structures of organic chromophores and polysaccharide substrates

图2. (a) NA和BP在甲醇中的吸收光谱和荧光光谱(3×10-5 mol/L); 不同浓度NA (b)和BP (c)在甲醇中的荧光光谱; (d) 77 K下NA和BP乙醇-甲醇(1∶9, V/V)溶液的发射光谱(λNAex=300 nm, λBPex=260 nm)

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)

图3. (a) CMC-Na/NA薄膜(w=1.9%)的吸收和发光光谱; (b) 不同掺杂浓度的CMC-Na/NA薄膜在空气中的发光光谱(λex=300 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

表1. CMC-Na/NA薄膜发光量子产率Φ、磷光量子产率ΦP和平均磷光寿命τav

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

表2. HA/NA和Chitosan/NA薄膜发光量子产率Φ和磷光量子产率ΦP

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

图4. 未掺杂和掺杂NA (w=0.5%)的CMC-Na、HA和Chitosan薄膜的红外光谱

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

图5. (a), (b)利用掺有1.9% (w) NA与BP的CMC-Na墨水打印太阳神鸟图案在关闭254 nm手提紫外灯后的磷光照片; (c) BP掺杂CMC-Na墨水打印理化所所徽图案在余辉变化照片(254 nm紫外灯激发)

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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