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Progress in Chemistry 2019, Vol. 31 Issue (11): 1560-1575 DOI: 10.7536/PC190812 Previous Articles   Next Articles

Clustering-Triggered Emission of Nonconventional Luminophores

Xiaohong Chen1,2, Yunzhong Wang2, Yongming Zhang2, Wangzhang Yuan2,**()   

  1. 1. Institute for Advanced Materials, North China Electric Power University, Beijing 102206, China
    2. School of Chemistry and Chemical Engineering, Shanghai Key Lab of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University, Shanghai 200240, China
  • Received: Online: Published:
  • Contact: Wangzhang Yuan
  • About author:
    ** E-mail:
  • Supported by:
    National Natural Science Foundation of China(51822303); Postdoctoral Innovative Talent Support Program of China(BX20190112)
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Intrinsic emission from nonconventional luminophores without classic remarkable conjugation has aroused increasing attention due to its significant fundamental importance and promising applications. These nonconventional luminophores generally contain the heteroatoms(i.e. N, O, S, P), unsaturated units of C≡N, C=O, C=C, etc., and their grouped moieties(i.e. hydroxyl, amino, ester, anhydride, amide, uramido, oxime, sulfone). In recent years, despite great progress has been achieved, the emission mechanism still remains under debate. Previously, we proposed the clustering-triggered emission(CTE) mechanism, namely the clustering of nonconventional chromophores with π and n electrons and subsequent through space conjugation result in extended electron delocalization and conformation rigidification, to rationalize the emission. Herein, based on the CTE mechanism, we review such typical emission characteristics of nonconventional luminophores as concentration enhanced emission, aggregation-induced emission(AIE), excitation-dependent emission, and phosphorescence. It is also noted that CTE mechanism can be used to rationalize the photophysical behaviors of different types of nonconventional luminophores of natural products, synthetic compounds, and biomolecules. Furthermore, it is also helpful to guide the rational discovery or design of new nonconventional luminogens. In addition, we briefly summarize the progress of different kinds of nonconventional luminophores. Finally, the perspectives of this emerging area are also discussed.

Key words: nonconventional luminophores, clustering-triggered emission, phosphorescence, through space conjugation, conformation rigidification
Fig. 1 (a) Photograph of rice taken under 365 nm UV light and its emission spectrum(λex=300 nm).(b) Photographs of the solid powders of starch and cellulose taken under 365 nm UV light[22]. Copyright 2013, Springer
Fig. 2 (a) Structures of starch, cellulose and some other natural saccharide products.(b) Single crystal structure of D-(+)-glucose and its schematic intra- and intermolecular O…O interactions.(c) Exampled 3D O…O short contacts in the D-(+)-glucose crystal
Fig. 3 (a) Photographs taken under 365 nm UV light and(b) emission spectra(λex=348 nm) of PAN/DMF solutions at varying concentrations.(c) Photographs of the solid powders and film of PAN taken under 365 nm UV light.(d) Emission spectra of 2 M PAN/DMF solution with varying λex values[57]. Copyright 2016, Wiley
Fig. 4 (a) Photographs of 1.25×10-4 M PAN/DMF taken at 77 K under 365 nm UV light or after ceasing the UV irradiation.(b) Photographs taken at room temperature under 365 nm UV light and(c) emission spectra and peak intensities of 1.25×10-5 M PAN in DMF and DMF/DCM mixtures.(d) Schematic illustration of possible electronic interactions in cyano clusters [57]. Copyright 2016, Wiley
Fig. 5 Structures of hyperbranched and linear PEIs and their photographs taken under UV irradiation[65]. Copyright 2009, Wiley
Fig. 6 (a) Photographs taken under UV irradiation and(b) emission spectra of hyperbranched PEI/ethanol solutions at varying concentrations[14]. Copyright 2017, Wiley
Fig. 7 Photographs taken under UV irradiation and(b) emission spectra of aqueous L-Lys solutions at varying concentrations[26]. Copyright 2018, Springer
Fig. 8 (a) Structure and schematic diagram of electronic interactions among different groups of HPS.(b) Photographs taken under 365 nm UV light and(c) excitation and emission spectra of HPS/ethanol solutions at varying concentrations[30].Copyright 2019, American Chemical Society
Fig. 9 (a) Structure and emission spectra of THF solution and nanosuspension in n-butyl acetate for PMV.(b) Luminescent photographs of THF solution(Ⅰ) and nanosuspensions of PMV with PMV concentration of 0.05 wt%(Ⅱ), 0.1 wt%(Ⅲ), and 1 wt%(Ⅳ).(c) SEM image of the nanoparticles[53]
Fig. 10 (a) Photographs of HOX/ethanol solutions at varying concentrations and HOX solids taken under UV light.(b) Single crystal structure of HOX and intermolecular interactions among nonconventional chromophores around one molecule.(c) Exampled through space electronic communications among C=N…O units in HOX crystal[24] Copyright 2017, Royal Society of Chemistry
Fig. 11 (a) Synthetic route to linear(l) and hyperbranched(hb) PAMAMs. Emission spectra and photographs taken under 365 nm UV light of (b) l-PAMAM and (c) hb-PAMAM in dilute aqueous solution(dash) and in 5/95(V/V) water/acetone mixture. Concentration=10 μg·mL-1, λex =380 nm. Emission spectra of (d) l-PAMAM and (e) hb-PAMAM films with different λex values as indicated. Inset: Luminescent microscopy photographs of PAMAM films taken under illumination of UV(top), blue(media), and green(bottom) lights[19]. Copyright 2015, Springer
Fig. 12 (a) Photographs of concentrated solutions of(a) PAN/DMF[57] and(b) aqueous L-Lys[26] taken at 77 K under 365 nm UV light or after ceasing the UV irradiation(a). Copyright 2016, wiley,(b) Copyright 2018, Springer
Fig. 13 (a) Structure of ε-PLL and the photograph of its powders taken under 365 nm UV light or after ceasing the irradiation.(b) Normalized emission spectra of ε-PLL powders with td of 0(solid line) and 0.1 ms(dash line) under varying λex[26]. Copyright 2018, Springer
Fig. 14 (a) Photographs of CAA solids taken under room light, 365 nm UV light or after ceasing the UV irradiation.(b) Single crystal structure of CAA and its schematic intra/intermolecular interactions among cyano and carboxyl groups.(c) Exampled 3D electronic interactions(through space conjugation) among cyano and carboxyl units in CAA crystals[27]. Copyright 2018, Royal Society of Chemistry
Fig. 15 (a) Structures of PEG, F127, and xylitol.(b) Photographs of the solid powders of F127, PEG, and xylitol taken under 312 nm UV light or after ceasing the UV irradiation at 77 K.(c) Photograph of xylitol powders taken at room temperature after ceasing the 312 nm UV irradiation, and partial electronic channels of O···O short contacts in xylitol crystals[29]. Copyright 2018, Royal Society of Chemistry
Fig. 16 (a) Structures and(b) photographs taken under 365 nm UV irradiation of MCC, HEC, HPC, CA, and C-CNC powders.(c) Delayed emission spectra of MCC solids at 77 K with different λex[42]. Copyright 2019, Springer
Fig. 17 (a) Structure of SA and photographs of solid powders, cast film, and Ca2+ crosslinked film taken under 312 nm UV light or after ceasing the irradiation.(b) Demonstration of the application of SA in anticounterfeiting[41]. Copyright 2018, American Chemical Society
Fig. 18 Structure and photographs of solid powders taken under UV light for(a) PU1~PU4[32] and(b) P1~P3[33]. Copyright 2019, Royal Society of Chemistry
Fig. 19 (a) HBPC with unreacted hydroxyl groups and(b~d) illustration of the formation of HBPC clusters in aqueous solution. TEM and luminescent images of (e) 5 and(f) 50 mg·mL-1 HBPC aqueous solutions[31]. Copyright 2017, Wiley
Fig. 20 (a) Structures and photographs of the solids taken under UV light or after ceasing the UV irradiation of PAA, PAM, and PNIPAM at ambient conditions.(b) Photographs of PNIPAM powders taken under UV light or after ceasing the UV irradiation under nitrogen(upper) or in vacuum(lower)[25]. Copyright 2019, Royal Society of Chemistry
Fig. 21 (a) Exampled nonaromatic amino acids and photographs of their recrystallized solids taken under 365 nm UV light.(b) Crystal structure of L-Ser with denoted intermolecular interactions around one molecule.(c) Fragmental 3D through space electronic communication channel in the L-Ser crystals [26]. Copyright 2018, Springer
Fig. 22 (a) Single crystal structure of BSA[83].(b) Photographs taken under 365 nm UV light or after ceasing the irradiation for aqueous solutions, solid powders, and a tablet of BSA.(c) Demonstration of the application of BSA in anticounterfeiting and oxygen sensing[44]. Copyright 2019, Wiley
Fig. 23 (a) Structure of PMVP and photographs taken under 365 nm UV light of(b) DMSO solutions(1 mg·mL-1) and(c) solid powders for PMVP with different molecular weights[34]. Copyright 2017, Royal Society of Chemistry
Fig. 24 Preparation strategy of new photoluminescent polymers and their luminescent photographs[36]. Copyright 2019, Royal Society of Chemistry
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