Supramolecular Polymer-Based Fluorescent Microfibers for

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Supramolecular Polymer based Fluorescent Microfibers for Switchable Optical Waveguides Cai-Li Sun, Zhenhua Gao, Kun-Xu Teng, Li-Ya Niu, Yu-Zhe Chen, Yong Sheng Zhao, and Qing-Zheng Yang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b08490 • Publication Date (Web): 10 Jul 2018 Downloaded from http://pubs.acs.org on July 10, 2018

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ACS Applied Materials & Interfaces

Supramolecular Polymer based Fluorescent Microfibers for Switchable Optical Waveguides Cai-Li Sun,†,ǁ Zhenhua Gao,‡,ǁ Kun-Xu Teng,† Li-Ya Niu,†Yu-Zhe Chen,§ Yong Sheng Zhao,*, ‡ and Qing-Zheng Yang*,† †

Key Laboratory of Radiopharmaceuticals, Ministry of Education, College of Chemistry, Beijing

Normal University, Beijing 100875, China ‡

CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences,

Beijing 100190, China §

Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute

of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China KEYWORDS: supramolecular polymers, optical waveguide, microfibers, pillararene, dithienylethene.

ABSTRACT: We report the switchable optical waveguide microfibers based on fluorescent supramolecular polymer for the first time. The pillar[5]arene-based supramolecular polymeric microfibers were prepared easily from the viscous solution of bispillar[5]arene host (bisP5A) and diphenylanthracene-derived guest (GD). The resulting microfibers can act as active optical

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waveguide material with long propagation distance (400 µm) and low optical propagation loss (0.01 dB/µm). When photoresponsive dithienylethene-derived guest (GDTE) was added, the resulting ternary microfibers show switchable optical waveguide by the non-invasion control of UV/Vis light with negligible fatigue over 4 cycles. This convenient preparation method is also applied for the quadruple-hydrogen-bonded fluorescent supramolecular polymeric microfibers which imply good light propagation property with optical-loss coefficient of 0.02 dB/µm.

INTRODUCTION Active optical micro/nanoscaled waveguides generate and propagate light at ever diminishing scale.1-2 They represent attractive building blocks for connecting light-emitting and lightdetecting elements in miniaturized photonic integrations. Controlling the flow of light at the micro/nanoscale is a promising direction to fully exploit the potential function of optical waveguides.3 Most reported micro/nanoscaled optical waveguides have focused on inorganic semiconductor micro/nanofibrillar

waveguides,4-8

organic

waveguides20-23.

micro/nanocrystalline9-19

Compared

with

inorganic

and

counterparts,

polymeric organic

micro/nanomaterials are able to realize the tunable performance of optical waveguide by employing cooperative nanocrystal of multiple components or doped copolymer nanofiber.24-26 However, cooperative nanocrystals are always prepared under harsh conditions while covalent conjugated polymer nanofibers suffer from the tedious chemical modiﬁcation. Fluorescent supramolecular polymers formed from low molecular-weight monomers offer considerable advantages over currently-used organic materials as building blocks for micro/nanoscaled optical waveguides.27-31 Firstly, the directional noncovalent interactions in


2

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fluorescent supramolecular polymers enable chromophoric monomers to aggregate orderly,29 providing potentiality in optical waveguide. Secondly, supramolecular polymers have superior synthesis to traditional covalent polymers as well as better processability than both organic cooperative nanocrystals and covalent polymers. Thirdly and most importantly, the introduction of

responsive

monomers,

including

non-invasion

photoresponsive

unites,32-36

into

supramolecular polymers is easy to realize due to the dynamic nature of noncovalent interaction,37-41 making the light propagation behavior easily tunable. Despite the great potential for manipulation of propagation behavior, optical waveguides based on fluorescent supramolecular polymers remain largely unexplored. Only one prior example existed, in which Wang and co-workers combined cooperative supramolecular polymerization of platinum acetylides and electrospinning techniques to afford fluorescent microfibers displaying active optical waveguide with extremely low optical loss.42 This result demonstrated supramolecular polymer as a promising candidate for optical waveguide and inspired us to design switchable active optical waveguide microfibers by utilizing dynamic and responsive nature of fluorescent supramolecular polymers. Herein, we report the fluorescent supramolecular polymers based microfibers with switchable active optical waveguide properties. The supramolecular polymeric microfibers were drawn from concentrated solution of supramolecular polymers comprised of bispillar[5]arene (bisP5A) and emissive diphenylanthracene-derivative (GD) (Figure 1a). The resulting microfibers manifest excellent active optical waveguide property with very low optical propagation loss. The switchable optical waveguide was achieved by the photoisomerization of dithienylethene moieties for the supramolecular copolymeric microfibers formed by the introduction of dithienylethene-based guest (GDTE). RESULTS AND DISCUSSION


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Preparation of fluorescent microfibers based on supramolecular polymer of bisP5A and GD. The supramolecular polymers are formed by the strong host-guest interaction of the pillar[5]rene (a kind of recently developed macrocyclic hosts, showing versatile complexation properties and wide potential applications43-51) based host molecule bisP5A and guest molecule GD embodied a pair of cyanoalkyl triazoles whose binding constant toward pillar[5]arene is 1.2 × 104 M 1

-1

in CHCl3.52-53 The supramolecular polymerization is confirmed by diffusion-ordered

H NMR spectroscopy (DOSY) (Figure S1a) and viscometry (Figure S1b). Figure S1b shows a

critical polymerization concentration (CPC, ca. 12 mM) for the solution of bisP5A and GD, above which the viscosity of solution increased with the increase of concentration in a nonlinear growth manner, revealing the formation of supramolecular polymers. The high viscosity of supramolecular polymer solution is the crucial factor for fabrication of microfibers. We used needle tip to draw a rod-like fiber from the CHCl3 solution of bisP5A and GD at high concentration (600 mM). Scanning electronic microscopy (SEM) images reveal the smooth surface of fiber and regular diameter of ca. 12 µm (Figure 1b, c). This microfiber is easily cut into appropriate-length fibers under optical microscopy. GD is a diphenylanthracene derivative and possesses characteristic photophysics with absorbance at 378 nm and fluorescence at 425 nm in CHCl3 (Figure S2). Most aggregated diphenylanthracenes are vulnerable to photoluminescence quenching, however, the aggregated assemblies of GD and bisP5A show strong emissive owning to the steric bulk of pillar[5]arene.53 The fibers also demonstrate intense blue emission under UV irradiation (Figure 1d). Fluorescence microscopy image exhibits bright emission spots at both ends and relatively weak emission from the body, suggesting the optical energy can propagate efficiently along the axial direction (Figure 1e).


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Figure 1. (a) Chemical structures of bisP5A and GD. (b) The SEM image of fluorescent supramolecular polymeric microfiber of bisP5A and GD. (c) Magnification of (b) indicating the smooth surface of microfiber. (d) The normalized absorption and fluorescence spectra of fluorescent supramolecular polymeric microfiber of bisP5A and GD (λexc = 378 nm). (e) Fluorescence microscopy image of supramolecular polymeric microfibers of bisP5A and GD. Optical waveguide of supramolecular polymeric microfibers based on bisP5A and GD. Spatially resolved fluorescence imaging and spectroscopy measurements were performed by locally exciting a single wire with a 375 nm focused laser beam (Figure S3). Figure 2a shows the micro-area waveguide fluorescence images obtained from a microfiber by accurately shifting the excitation laser spots. The length of used microfiber is approximately 400 µm, much longer than most reported organic micro/nanocrystalline waveguide materials, providing a chance to investigate the long-distance light propagation. The distance dependent emission spectra of the microfiber indicate the emission intensity of GD at the tip decays with the increase of


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propagation distance (Figure 2b). The decay is exponential with the increase of propagation distance as shown in Figure 2c, which is a characteristic of active waveguides. The optical-loss coefficient (R) was calculated by single-exponential fitting Itip/Ibody=Aexp(-RD), where Itip is emissive intensity at the detected emitting tip, Ibody is the intensity at the excited site along the microfiber, and D is the distance between the excited site and the emitting tip. Accordingly, R = 0.01 dB /µm at 450 nm, which is much lower than the value for many other organic micro/nanocrystalline and polymeric micro/nanofibrillar waveguides. There are two important factors that may contribute to the excellent optical waveguide behavior of the microfiber. Firstly, the overlap of fluorescence and absorption spectra of microfiber is very narrow (Figure 1d), diminishing the reabsorption of light during propagation along the wire effectively. Secondly, the good solubility of bisP5A and GD and high viscosity of supramolecular polymer make the smooth surface of microfiber, minimizing the optical loss caused by scattering.

Figure 2. (a) Bright-field and fluorescence images obtained from a supramolecular polymeric microfiber of bisP5A and GD by exciting the microfiber at different positions. Scale bar = 100 µm. (b) Spatially resolved fluorescence spectra from the tip of the microfiber for different separation distances between the excitation site and tip of the microfiber shown in (a). (c) The ratio of the fluorescent intensity at 450 nm versus the propagation distance. The curve was fitted by an exponential decay function Itip/Ibody=Aexp(-RD).


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Switchable optical waveguide of supramolecular polymeric microfibers based on ternary monomers: bisP5A, GD and GDTE. By using the dynamic character of supramolecular polymers, we designed dithienylethene-based guest molecular GDTE as a third monomer to tune the fluorescence of supramolecular polymeric materials and their light propagation behavior. We grafted two cyanoalkyl triazole moieties onto dithienylethene to afford GDTE. 1H NMR spectra manifest the complexation of GDTE with bisP5A (Figure S4). The dithienylethene moiety has reversible ring-open and ring-closed isomers showing distinct absorption spectra shape.34, 54-57 The GDTE we prepared are ring-open isomer which can convert to ring-closed isomer (GDTEc) under the irradiation of UV light. Only ring-closed GDTE-c can serve as the energy acceptor of GD and quench the fluorescence of GD on account of the spectra overlap between the absorption of GDTE-c and the emission of GD (Figure 3a and Figure S5). The photo-controlled behavior was firstly confirmed on the water-dispersible supramolecular copolymeric nanoparticles of bisP5A, GDTE and GD. We used the bisP5A, GDTE and GD with ratio of 1.25: 0.25: 1.0 in mole to prepare nanoparticles by microemulsion method (Figure S6).58 The initial absorption spectrum of aqueous dispersions of nanoparticles comprised two bands: a high tail peak corresponding to the mixture of absorption bands of ring-open GDTE and bisP[5]A and scattering of nanoparticles; a typical absorption of GD with the maximum absorption at 378 nm. A new absorption band at 527 nm appeared upon irradiation with UV light (310 nm), corresponding to that of dithienylethene in the ring-closed state (Figure 3b). This isomer therefore quenched the fluorescence of GD in nanoparticles, leading to significant fluorescence decrease by up to 77% (Figure 3d). Irradiation of the resulting nanoparticles at visible light (520 nm) could switch off this energy transfer process because of the photoisomerization of GDTE


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from ring-closed dithienylethene to ring-open isomer (Figure 3c). As a result, the fluorescence of GD was recovered (Figure 3e).

Figure 3. (a) Photo-controlled ring-open and ring-closed isomerization of GDTE and GDTE-c. Time resolved absorption (b) and fluorescence (d) spectra of aqueous dispersion of supramolecular copolymeric nanoparticles of bisP5A, GDTE and GD (1.25: 0.25: 1.0 in mole) upon irradiation with UV light. Time resolved absorption (c) and fluorescence (e) spectra of the resulting aqueous dispersion of supramolecular copolymeric nanoparticles upon irradiation with visible light. The excitation wavelengths in (d) and (e) are 378 nm. Inspired by the switchable fluorescence of supramolecular polymeric nanoparticles, we transferred our attention back to fluorescent supramolecular polymeric microfibers. Considering the same guest part possessed by GD and GDTE, the participation of GDTE merely alters the assembly behavior. The microfibers were drawn from ternary solution of bisP5A, GDTE and


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GD (1.25: 0.25: 1.0 in mole) in CHCl3 and characterized by SEM (Figure S7). We excited a single fiber at one tip with 375 nm focused laser beam and clear blue emission was detected at the other tip, indicating the light propagation of this microfiber (Figure 4a upper). The microfiber was then exposed under UV light (330-380 nm) for 3 min. However, after the irradiation the light propagation of the microfiber was inhibited (Figure 4a below). As shown in Figure 4b, the final emissive intensity of far tip decreased by ~47%. It was because UV irradiation induced the conversion from GDTE to GDTE-c and the resulting absorption quenched the fluorescence of GD, hindering light propagation. Remarkably, the light propagation could be turned on again by irradiating the microfiber with visible light (510-560 nm) and the photoluminescence at the far tip was recovered. By using the ternary supramolecular polymeric microfibers with higher fraction of GDTE (ratio of bisP5A, GDTE and GD = 1.40: 0.40: 1.0 in mole), the light propagation behavior was further switched off upon irradiation under UV light, with the emissive intensity of detected tip decreased by ~75% (Figure S8). The reversibility of photo-controlled switch was monitored successfully by alternating irradiation of this microfiber with UV/Vis light over at least 4 cycles with negligible fatigue (Figure 4c).

Figure 4. (a) Bright-field and fluorescence images obtained from a fluorescent supramolecular polymeric microfiber of bisP5A, GDTE and GD (1.25: 0.25: 1.0 in mole) by exciting one tip of the microfiber. Scale bar = 100 µm. The upper one is the initial image and the below is the image


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of microfiber after 3 min UV irradiation. The emission of detected tip can recover by another 3 min Vis irradiation. (b) The initial fluorescence spectrum of the microfiber and that of the microfiber after irradiation with UV light. (c) The switch cycles of fluorescence at the right tip upon UV irradiation and subsequent recovery upon Vis irradiation. Optical waveguide of supramolecular polymeric microfibers based on UPyD. We finally expanded this method of constructing micro-scale active waveguides to fluorescent supramolecular polymers based on other noncovalent interaction, for example, quadruplehydrogen-bonded fluorescent supramolecular polymers. Diphenylanthracene derivative UPyD containing self-complementary ureidopyrimidinone motifs was synthesized (Ka = 6 × 107 M-1 in CHCl3, Figure 5).58-60 We drew fluorescent supramolecular polymeric microfibers from the CH2Cl2 solution of UPyD (Figure S9). The light propagation property of the materials was also evaluated by micro-area waveguide fluorescence images and spectra obtained from a microfiber by shifting the excitation laser spots and the spatially resolved emission spectra. The optical-loss coefficient was 0.02 dB/µm at 450 nm, slightly higher than that of GD⊂bisP5A-based microfiber. The relative coarse surface of UPyD-based fiber probably accounts for this difference in optical-loss coefficients.


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Figure 5. (a) Chemical structure of UPyD. (b) Bright-field and fluorescence images obtained from a fluorescent supramolecular polymeric microfiber of UPyD by exciting the microfiber at different positions. Scale bar = 50 µm. (c) Spatially resolved fluorescence spectra from the tip of the microfiber for different separation distances between the excitation site and tip of the microfiber shown in (a). (d) The ratio of the fluorescent intensity at 450 nm versus the propagation distance. The curve was fitted by an exponential decay function Itip/Ibody=Aexp(RD). CONCLUSION In summary, we described the fluorescent supramolecular polymeric microfibers with excellent active optical waveguide properties. These micro optical waveguides were prepared easily from the viscous solution of the supramolecular polymers. The long propagation distance of 400 µm and low optical-loss coefficient of 0.01 dB/µm were achieved. The dynamic and reversible noncovalent interactions of the supramolecular polymers allowed the introduction of photoresponsive monomer conveniently, resulting in non-invasion photo-controlled switch of optical waveguide by the reversible isomerization of the dithienylethene moieties. To the best of


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our knowledge, this is the first example to fabricate micro switchable waveguide based on the fluorescent supramolecular polymers by using their dynamic nature of noncovalent bond. This strategy may inspire the exploration of supramolecular polymer based controllable optical materials. EXPERIMENTAL SECTION Materials. Building blocks bisP5A, GD, and UPyD were synthesized according to the reported procedures.53, 58, 61 The synthesis of GDTE is described in the Supporting Information, Section 1. THF was distilled from sodium and benzophenone. Other chemicals and solvents were obtained from commercial suppliers and used without further purification. General methods. Column chromatography was performed over silica gel (200-300 mesh). 1D NMR spectra were recorded on JEOL Delta spectrophotometer at 25 °C and referenced to the solvent signal (400 MHz and 600 MHz for 1H NMR and 100 MHz for 13C NMR). 2D diffusionordered NMR (DOSY) spectra were conducted on Bruker Avance 600 spectrophotometer at 25 °C. High-resolution mass spectrometry experiments were recorded by Thermo Fisher Q-Exactive or Bruker Daltonics Apex IV FTMS. Viscosity measurements were performed with a microUbbelohde dilution viscometer at 25 °C in CHCl3. Water-dispersible supramolecular polymeric nanoparticles were prepared by injecting the 200 µL CHCl3 solution of monomers into cetyl trimethyl ammonium bromide (CTAB) aqueous solution (10 mL, 0.9 mM) followed by sonication on Scientz JY92-IIN ultrasonic disruptor. Scanning electron microscopic (SEM) images were obtained using a Hitachi S-4800 instrument. All optical spectra were recorded at room temperature. Absorption spectra were recorded on Hitachi UV-3900 spectrophotometer for liquid samples and Hitachi UH4150 for microfibers. Fluorescence spectra were determined on


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Hitachi F-4600 spectrophotometer for liquid samples and Edinburgh FLS980 spectrometer for microfibers. Optical waveguide measurements. A homemade micro-photoluminescence system was used to examine optical waveguide performances of the supramolecular polymeric microfiber (Figure S3). Bright-field optical images and fluorescence microscopy images were taken with an inverted fluorescence microscope (Nikon Ti-U). A focused 375 nm CW laser beam was employed to locally excite the supramolecular polymeric microfiber and the spatially resolved spectra were recorded with a monochrometer (Princeton Instrument Acton SP 2300i) connected with an EMCCD (Princeton Instrument ProEM 1600B). Microfiber was dispersed on a glass substrate. The excitation laser was filtered with a band-pass filter (330-380 nm) and focused on the microfiber with objective lens (5×, N. A. = 0.15; 10×, N. A. = 0.30). After passing through a dichroic mirror (DM 400 nm) and an emission filter (420 nm LP), the collected emission signal was focused by a group of lenses onto a removable iris. The output signal can be spatially selected by the iris and analyzed with a spectrometer. ASSOCIATED CONTENT Supporting Information. The following files are available free of charge. Experimental details including the synthesis of GDTE; DOSY and viscosity of the supramolecular polymers based on bisP5A and GD; the host-guest interaction of bisP5A and GDTE by 1H NMR; schematic demonstration of the experimental setup for optical waveguide measurement; absorption and fluorescence spectra of GD; absorption spectra of ring-open


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GDTE and ring-closed GDTE-c; SEM images of microfibers and nanoparticles; 1H NMR and 13

C NMR copies of bisP5A, GD and GDTE (PDF)

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (Q.-Z. Y.). *E-mail: [email protected] (Y. S. Z.). Author Contributions ǁ

C.-L. S. and Z. G. contributed equally.

Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We are grateful for financial support from the National Natural Science Foundation of China (21525206, 21790364, 21472202). REFERENCES (1) Zhang, C.; Yan, Y.; Zhao, Y. S.; Yao, J. From Molecular Design and Materials Construction to Organic Nanophotonic Devices. Acc. Chem. Res. 2014, 47, 3448-3458. (2) Yan, Y.; Zhao, Y. S. Organic Nanophotonics: from Controllable Assembly of Functional Molecules to Low-Dimensional Materials with Desired Photonic Properties. Chem. Soc. Rev. 2014, 43, 4325-4340. (3) Zhang, C.; Zhao, Y. S.; Yao, J. Optical Waveguides at Micro/Nanoscale based on Functional Small Organic Molecules. Phys. Chem. Chem. Phys. 2011, 13, 9060-9073.


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Supramolecular Polymer-Based Fluorescent Microfibers for

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