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Synthesis of network polymer emitters: tunable detection of chemicals by geometric design

Abstract

Conjugated network polymer emitters are potential materials for use as solid detectors of chemicals. We demonstrated the synthesis of fluorescent network polymers through a facile route. Solid-state fluorescent network polymer emitters were synthesized through the Knoevenagel polycondensation of an arylaldehyde (tris(p-formylphenyl)amine) with an arylacetonitrile (phenylenediacetonitrile) in good yields. The molecular structure based on the electron-donor triphenylamine and electron-acceptor cyano-substituted phenylene-vinylene showed a highly efficient solid-state fluorescence. The synthesized model small molecule showed a well-defined solvatofluorochromism: the dielectric constants were εsol of approximately 0–50 at λfl of 480–560 nm. The response to solvent chemicals was also shown for the network polymers. Surprisingly, the network polymer linked with para-phenylene-vinylene was only responsive to the solvents with a low dielectric constant (εsol ca. <8) and nitrobenzene, for which εsol is approximately 35. This solvatofluorochromic behavior differed from that of the model compound. More interestingly, the network polymer linked with meta-phenylene-vinylene was responsive to the aromatic solvents only. Consequently, the characteristic chemoselectivity was observed by the geometric effect of the network structure.

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Acknowledgements

S.H. acknowledged a KAKENHI (Grant-in-Aid for Scientific Research B: no. 18H02052 and Grant-in Aid for Scientific Research in Innovative Areas “π-figuration”: no. 17H05171) of the Japan Society for the Promotion of Science (JSPS). T.K. also acknowledged a KAKENHI (Grant-in-Aid for Scientific Research C: no. 17K05891) of JSPS. This work was performed under the Cooperative Research Program of the "Network Joint Research Center for Materials and Devices.” We would like to thank Shimadzu for the HRMS measurements. We thank the Edanz Group (www.edanzediting.com/ac) for editing a draft of this manuscript.

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Correspondence to Shotaro Hayashi.

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Synthesis of Network Polymer Emitters: Tunable Detection of Chemicals by the Geometric Design

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