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Amplified circularly polarized luminescence enabled by photon upconversion in spin-coating cellulose matrix
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Lingxia Liua, c, Jinping Chena, Tianjun Yua, Rui Hub, Guoqiang Yangb, c, Yi Zeng*, a, c, Yi Li*, a, c
Chinese Chemical Letters | 2023, 34(3) : 107649
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Chinese Chemical Letters | 2023, 34(3): 107649
• Communication •
Amplified circularly polarized luminescence enabled by photon upconversion in spin-coating cellulose matrix
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Lingxia Liua, c, Jinping Chena, Tianjun Yua, Rui Hub, Guoqiang Yangb, c, Yi Zeng*, a, c, Yi Li*, a, c
Affiliations
  • aKey Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
  • bKey Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
  • cUniversity of Chinese Academy of Sciences, Beijing 100049, China
Published: 2023-03-15 doi: 10.1016/j.cclet.2022.06.072
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It is of great significance to construct organic circularly polarized luminescence systems (CPL) with large luminescence dissymmetry factors (glum) for practical applications. Here we report organic CPL systems constructed by merging triplet-triplet annihilation upconversion chromophores in cellulose matrices. The chirality of the matrix is transferred to the achiral chromophores of photon upconversion and then the multistep energy transfer processes of upconversion amplify glum. The glum value of upconversion CPL in the left-handed ethyl cellulose and the right-handed (acetyl) ethyl cellulose are up to +0.1 and −0.15, respectively. The study provides a straightforward approach for constructing solid organic upconversion CPL materials with large glum, which may expand the application potentials of organic chiroptical materials.

Circularly polarized luminescence  /  Photon upconversion  /  Cellulose  /  Chirality  /  Triplet-triplet annihilation
Lingxia Liu, Jinping Chen, Tianjun Yu, Rui Hu, Guoqiang Yang, Yi Zeng, Yi Li. Amplified circularly polarized luminescence enabled by photon upconversion in spin-coating cellulose matrix[J]. Chinese Chemical Letters, 2023 , 34 (3) : 107649 - . DOI: 10.1016/j.cclet.2022.06.072
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Circularly polarized luminescence (CPL) can provide significant information for advanced visual perception since it not only reveals excited-state properties of chiral systems, but also has a wide range of application prospects in chiral devices, enantioselective sensing systems, and biomedicine, such as 3D display, OLED materials, information storage and processing, CPL lasers and biological probes [1, 2]. Therefore, this field has received growing attention and become one of the hot spots in recent years. A core issue in developing CPL materials is achieving a large dissymmetric factor glum, which is calculated by glum = 2(IL – IR)/ (IL – IR), where IL and IR are the intensity of left- and right-handed circularly polarized emission intensity, respectively. The maximum value of glum is +2 or −2, which represents complete left- or right-handed CPL, respectively. Though having tunable emission and high emission efficiency, organic CPL systems usually present small glum of around 10−5~10−2, which hampers their applications. Various approaches have been developed to amplify asymmetric factors in organic systems, such as modification of highly emissive chromophore molecules with chiral groups, CPL induction by doping chiral molecules, assembly in supramolecular structures, photophysical process regulation including cascade energy transfer, charge transfer and photochemical upconversion [3-11].
To build an efficient CPL system, transfer and control of chirality from the molecular level to nanoscale and even macroscopic materials is the first step and the strategy of chiral co-assembly was proven to be effective [1]. In addition, the magnetic dipole moments and electric dipole moments of the excited organic molecules are sensitive to photophysical processes, through which CPL signals can be amplified [7]. Photon upconversion based on triplet-triplet annihilation upconversion (TTA-UC) involves photosensitizers and triplet energy acceptors and series energy transfer processes such as sensitization, triplet energy transfer and triplet-triplet annihilation [12-15]. Combination of TTA-UC technology and CPL design can construct upconversion CPL systems with amplified glum [4].
With the rising demand for sustainable clean energy technologies, as well as solidified material for practical applications, developing CPL materials with large glum through non-sophisticated methods is still an exciting endeavor in CPL research. Herein, we report solid organic CPL systems with large glum by combining cellulose matrix and photon upconversion materials. Solid biomaterials such as cellulose are considered as promising chiral optical matrices [16]. Photon upconversion based on TTA-UC proceeds through a series of energy transfer processes where glum could be amplified. It is envisioned that integrating the chirality transfer from cellulose matrices and amplification during upconversion would construct materials with intriguing CPL properties. The photosensitizer and triplet energy acceptor of TTA-UC are physically doped into the chiral cellulose chain and solidified in the chiral nematic structure through noncovalent interactions during spin-coating. The chiral matrices transfer chirality to the chromophores which generate amplified CPL via TTA-UC. The glum of the solid TTA-UC CPL systems from the left-handed and the right-handed matrix are up to +0.1 and −0.15, respectively (Scheme 1).
Ethyl cellulose (EC) or (acetyl) ethyl cellulose (AEC) with chiral skeleton and rigid helical structure can form a chiral nematic structure by self-assembling. The TTA-UC photosensitizer is octaethyl porphyrin platinum(Ⅱ) (PtOEP) and the triplet energy acceptor is 9, 10-diphenylanthracene (DPA) which can upconvert green excitation light into blue photons. The chloroform solution of the cellulose, PtOEP and DPA was prepared by spin coating onto glass slides, giving the TTA-UC CPL film. EC usually generates liquid crystal with a left-handed helical structure both in solvent and solid state [17-19]. The EC films without or with PtOEP and DPA doping were firstly investigated with polarized optical microscopy (POM) and scanning electron microscopy (SEM). For all EC films, clear birefringence phenomena displaying planar liquid crystal texture – Grandjean texture were observed under the POM as shown in Figs. 1a-d, indicating the helical axis of a chiral liquid crystal is parallel to the optical axis and the positive birefringence of EC liquid crystal [19]. Moreover, no chromophore crystal was observed in the transparent chiral EC films suggesting the good dispersity of chromophores in EC matrix. Brittle fractured by liquid nitrogen, the cross-sectional SEM images of the EC films present a rough cascaded fracture surface in Figs. 1e-h. The rich pore-like structure in microscale and certain long-range oriented texture in mesoscopic scale is mainly due to the twisted helical morphology and the rigidity of molecular chains of EC [20]. The possible interaction between the chromophores and the cellulose matrix was analyzed by attenuated total refraction Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray diffraction (XRD), respectively. The FTIR spectra of all samples show no evident difference (Fig. S2 in Supporting information) to the pure EC film. The XRD patterns of all samples (Fig. S3 in Supporting information) are broad and exhibit two wide amorphous diffraction peaks of the cellulose Ⅱ at around 10.5° and 20.5° [21, 22]. The results indicate that EC is mainly in an amorphous state. The chromophores interact with the matrix mainly by weak van der Waals forces, to form homogeneous films during solidification by spin-coating [23].
The upconversion emission spectra of those PtOEP/DPA@EC films were tested upon excitation by a 532 nm laser at 200 mW/cm2. A series of transparent PtOEP/DPA@EC films are prepared by fixing the molar ratio of DPA: PtOEP at 500:1, and increasing the doping concentration of DPA/EC from 0.25 wt% to 12.5 wt%. When the doping concentration of DPA ≥ 8.75 wt%, DPA began to segregate in EC film which hinders the chiral assembly process and weakens the TTA-UC intensity (Fig. S4 Supporting information). The chiral properties of PtOEP/DPA@EC film with optimal doping content of [DPA/EC] = 8.75 wt% were further investigated.
The CD spectra of DPA@EC film, PtOEP@EC film, and PtOEP/DPA@EC film were collected, respectively. In Figs. 2a-c, the CD signal at the maximum absorption of the triplet energy acceptor DPA at 340, 356, 375, 395 nm, and the photosensitizer PtOEP at 381 and 533 nm exhibited positive Cotton effect, respectively, which is consistent with the pure EC film. When a beam of circularly polarized light enters the EC film, the left-handed EC films prefer to reflect the left-handed circularly polarized light, so that the electric vibration vector of the light wave presents a positive left-handed signal [24]. CD spectra reveal the chiral absorption signal of the chromophore induced by the chiral matrix. In general, the interference of macroscopic anisotropies usually presents in solid samples, i.e., linear dichroism (LD) and linear birefringence (LB) properties providing certain contributions to the measured CD spectrum in thin films. Therefore, the crude CD signal of such a solid film is the sum of various contributions [25]. To exclude the interference of linear polarization absorption, CD and its synchronous linear dichroism (LD) were collected when the film is rotated by various degrees of 0°, 90°, 180°, 270° and 360°, respectively (Fig. S5 in Supporting information). The circular dichroic absorption signal of the film is far stronger than its linear polarization signal. And the original CD is similar to the flipped (rotated by 180°) sample, indicative of negligible LD and LB contribution.
The CPL spectra of DPA@EC, PtOEP@EC, and PtOEP/DPA@EC films were measured by a CPL-200 spectrometer, respectively. Obvious positive CPL signals of all EC films are observed as shown in Figs. 2d-f, indicating the CPL activity of chromophores endowed by the EC matrix. The glum values of DPA@EC, PtOEP@EC, and PtOEP/DPA@EC films are calculated to be +0.057, +0.04 and +0.10, respectively [26-28]. The TTA-UC film presents a significant enhancement in glum value due to the involvement of series energy transfer process during photon upconversion.
It has practical significance to achieve different chiral properties of chiral systems by controlling the chiral matrix. Since the commercial EC exhibits single left-handed chirality in chloroform. To construct CPL systems with different chirality, we prepared the EC derivative matrix AEC of different chirality by modifying its side chain group through a one-step acetylation reaction (Fig. S6 in Supporting information). FTIR (Fig. S7 in Supporting information) confirmed the -OH group of EC has been partially acetylated to produce AEC. With the increase of acetyl substitution, the helical distance of the cellulose chains increases, which leads to the decreasing twisting power of the chiral nematic mesophase. As a consequence, the originally left-handed helical structure turns into a right-handed arrangement [21]. Whether the CD signal of AEC is negative or not is related to the degree of its acetylation. The AEC sample prepared by 5 h acetylation of EC exhibits extensive negative signal compared to the EC film (Fig. 3a).
Chloroform solution of AEC was spin-coated on glass giving a thin film of the right-handed helical structure. Grandjean planar liquid crystal texture can be observed in pure AEC, DPA@AEC, PtOEP@AEC and PtOEP/DPA@AEC films under POM (Fig. S8 in Supporting information). Within the allowable range of errors, the CD signals of series of AEC films are negative (Fig. 3b, Figs. S9a and b in Supporting information), showing a significant negative Cotton effect. The reflective bands of negative chirality of AEC films indicate the characteristics of the right-handed chiral structure, which is opposite to all CD signals of films prepared with EC [29]. The doped AEC films present a negative CPL which is opposite to that of doped EC films. The glum of CPL from DPA@AEC, PtOEP@AEC, and PtOEP/DPA@AEC films are measured to be −0.04, −0.017, and −0.15, respectively (Fig. 3c and Fig. S9 in Supporting information). It is worth noticing that both in the EC or the AEC films, the glum of the upconversion system is significantly larger than the films doped with DPA or PtOEP only (Fig. 3d). the amplification of glum in TTA-UC systems can be explained in the amplified magnetic-dipole transition moment through the TTA process and depressed electric-dipole moments by inter- or intramolecular radiationless energy transfer, both of which resulted in the increase of CPL glum in the TTA-UC system [30].
In summary, organic CPL systems with large glum based on cellulose matrix and photon upconversion chromophores were constructed by simply spin-coating. The achiral sensitizer and acceptor of TTA-UC are endowed with chirality from the cellulose matrix and CPL from the chromophore is significantly amplified owing to the energy transfer processes of TTA-UC. By applying the left-handed ethyl cellulose or the right-handed (acetyl) ethyl cellulose as the chiral matrix, CPL glum up to +0.1 and −0.15 are achieved, respectively. This work proposes a straightforward approach for constructing solid organic upconversion CPL materials with large glum, which expands the research scope and application potentials of organic chiroptical materials.
Declaration of competing interest
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The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
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We are grateful for the financial support from the National Natural Science Foundation of China (Nos. 21673264, 21573266, 21672226 and 22090012) and the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Nos. 2017032 and 2020035).
Supplementary materials
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Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.cclet.2022.06.072.
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Year 2023 volume 34 Issue 3
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Article Info
doi: 10.1016/j.cclet.2022.06.072
  • Receive Date：2022-04-20
  • Online Date：2025-11-21
  • Published：2023-03-15
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  • Received：2022-04-20
  • Revised：2022-06-16
  • Accepted：2022-06-26
Affiliations
    aKey Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
    bKey Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
    cUniversity of Chinese Academy of Sciences, Beijing 100049, China
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表12种不同金属材料的力学参数
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Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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