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Preparation of a Germole-Containing Π-Conjugated Polymer by the Te–Li

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Preparation of a Germole-Containing Π-Conjugated Polymer by the Te–Li Zheng et al. NPG Asia Materials (2020) 12:41 https://doi.org/10.1038/s41427-020-0224-9 NPG Asia Materials ARTICLE Open Access Preparation of a germole-containing π-conjugated polymer by the Te–Li exchange reaction of a tellurophene-containing polymer Feng Zheng1,Sia-ErTan1, Yuki Yanamoto1, Naoki Shida 1, Hiroki Nishiyama1, Shinsuke Inagi1 and Ikuyoshi Tomita 1 Abstract The synthesis and optoelectronic functions of a germole-containing π-conjugated polymer prepared by the reaction of a lithiated polymer precursor are described. A regioregular organometallic polymer having 1,4-dilithio-1,3-butadiene and 9,9-dioctylfluorene-2,7-diyl units was generated by the reaction of a tellurophene-containing polymer having a number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of 5900 and 1.9, respectively, with n-butyllithium (2.4 equiv) at −78 to −60 °C for 3 h. The prepared lithiated polymer was reacted with dimethylgermanium dichloride (1.5 equiv) at −60 °C to ambient temperature for 12 h in tetrahydrofuran to produce a π-conjugated polymer possessing 1,1-dimethylgermole-2,5-diyl units in 76% yield (Mn = 4400 and Mw/Mn = 1.7). The absorption maximum and onset of the obtained polymer were observed at 465 and 535 nm, respectively, in the UV-vis spectrum, from which the optical band gap of the polymer was estimated to be 2.31 eV. In the photoluminescence spectrum, the obtained polymer exhibits green fluorescence with an emission maximum of 547 nm and a quantum yield of 0.04. The chemical interaction of the dimethylgermole-containing π-conjugated polymer with fluoride was also examined in terms of the changes observed in the UV-vis absorption spectra. 1234567890():,; 1234567890():,; 1234567890():,; 1234567890():,; Introduction transporting properties of these polymers were demon- π-Conjugated polymers are attractive materials for the strated in organic EL devices. This unique electronic construction of functional organic optoelectronic devi- function is explained by the low-lying LUMO energy – ces1 4. According to the theoretical calculations carried levels due to σ*–π* orbital interactions6,7. Stannole- out by Lagowski and coworkers, the incorporation of containing polymers have also been prepared by Stau- heteroatoms into the main chain of π-conjugated poly- bitz and coworkers and independently by us by using mers provides us the chance to alter the energy levels of highly tin‐selective Stille coupling reactions and by the the highest occupied molecular orbital (HOMO) and transformation of organotitanium polymers, respectively. lowest unoccupied molecular orbital (LUMO). For As also expected from the theoretical calculations, these example, polymers containing heteroles of group 14 ele- polymers exhibited low-lying LUMO energy levels due to ments, such as poly(silole)s, are predicted to possess both σ*–π* orbital interactions8,9. low LUMO and high HOMO levels that would be suitable Germole derivatives, heteroles containing the germa- for both n- and p-type semiconducting materials5. Silole- nium atom (Ge), are also reported to possess low-lying containing polymers have been prepared by Yamaguchi, LUMO energy levels and narrow energy band gaps that Tamao, and their coworkers, and the excellent electron- are comparable to those of the silole and stannole deri- vatives10. Although germole-containing π-conjugated materials are also attractive for many optoelectronic Correspondence: Ikuyoshi Tomita ([email protected]) applications, within the knowledge of the authors, only 1Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Nagatsuda-cho one previous synthetic work has been reported by Tilley 4259-G1-9, Midori-ku, Yokohama 226-8502, Japan © The Author(s) 2020 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a linktotheCreativeCommons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. Zheng et al. NPG Asia Materials (2020) 12:41 Page 2 of 7 and coworkers in which germole-containing polymers (Me2GeCl2) was obtained from Tokyo Chemical Industry. were prepared by the nickel-mediated cross-coupling Tetrahydrofuran (THF) was dried over sodium benzo- polymerization of germole-containing monomers pre- phenone ketyl and distilled under nitrogen. The reactions pared from zirconacycle intermediates. Nevertheless, the were carried out under argon, and all reagents for pre- properties of germole-containing polymers have not yet cipitation and analyses were used as received. been fully demonstrated11. Since the size of the elements would affect the intermolecular packing of the ring sys- Apparatus tems, the properties of the germole might be different Nuclear magnetic resonance spectra were obtained on from those of the silole and stannole. In addition, due to a JEOL ECP300 spectrometer in CDCl3 (300 and d-block contraction, the electronegativity of Ge is larger 75 MHz for 1HNMRand13C NMR, respectively). than that of Si and much closer to that of C, which Tetramethylsilane was used as an internal standard for reduces the polarization of C–Ge bonds12,13. 1H NMR spectra. Size exclusion chromatography (SEC) In the course of our studies on the synthesis and measurements were performed on a Shimadzu LC-10AS transformations of regioregular organotitanium poly- liquid chromatograph equipped with Tosoh TSK-gel – mers14 19, which are obtained by the reaction of diynes GMHHR-M tandem columns using chloroform and a low-valent titanium complex, we anticipated that (CHCl3) as the eluent at 35 °C. Polystyrene standards germole-containing π-conjugated polymers are also were used for the calibration. Ultraviolet-visible (UV- obtained by transformation with germanium-containing vis) absorption spectra and photoluminescence (PL) electrophilic reagents. In our attempts, however, the spectra were measured in CHCl3 on a Shimadzu UV- efficiency of the transformation was not sufficient to 3100PC and a Shimadzu RF-6000PC spectrometer. carry out the polymer reactions. Very recently, we Fourier transform infrared (FT-IR) spectra were mea- reported the synthesis of highly reactive organolithium sured on a Shimadzu IRSpirit spectrophotometer. High- polymers via the Te–Li exchange reaction of resolution mass spectra (HR-MS) were obtained on a tellurophene-containing polymers. That is, tellurophene- JEOL JMS-SX102A spectrometer. Electrochemical containing polymers, which were prepared by the post- measurements were recorded on a VersaSTAT3 (Prin- element transformation of organotitanium polymers20, ceton Applied Research) potentiostat using a platinum were subjected to the tellurium–lithium exchange pro- (Pt) disk working electrode (d = 1.6 mm, BAS, Japan), a cess to generate organolithium polymers21,22. The highly spiral Pt wire auxiliary electrode, and a silver (Ag) wire reactive nature of the organolithium polymers was reference electrode under a nitrogen stream. The demonstrated in part by the reaction with tributyltin molecular orbital density functional theory (DFT) cal- chloride to produce tributyltin-substituted π-conjugated culations were performed by using the Becke’s three- polymers, which have seldom been accessible by trans- parameter Lee–Yang–Parr hybrid (B3LYP) functional formation of organotitanium polymers. Because of the and the 6–31G(d) basis set in the Gaussian16 program higher reactivity of the organolithium polymers com- package23. pared to that of the organotitanium polymers, we expect that unprecedented π-conjugated polymers containing Experimental procedures more versatile elements and functional groups would be Synthesis of 1,1-dimethyl-2,5-diphenylgermole (3) accessible by means of the post-element transformation To a 20 mL two-necked test tube containing 1 (0.040 g, technique. To establish a new synthetic route and to 0.12 mmol) and THF (5.0 mL), was added n-butyllithium produce attractive germole-containing π-conjugated (2.4 equiv, 1.6 M, 0.18 mL, 0.29 mmol) at −78 °C, and the polymers, we describe herein the reaction of an organo- mixture was gradually warmed to −60 °C. After stirring at lithium polymer generated by the Te–Li transformation −60 °C for 3 h, the obtained lithiated intermediate (2) was of a tellurophene-containing polymer with dimethylger- reacted with Me2GeCl2 (1.5 equiv, 0.031 g, 0.18 mmol), manium dichloride. The optoelectronic features of the and the mixture was slowly warmed to ambient tem- germole-containing polymer are also described to reveal perature and stirred for an additional 12 h. Then, the its potential applications. resulting reaction mixture was poured into water (10 mL), the organic layer was collected, and the aqueous phase Materials and methods was extracted three times with dichloromethane (CH2Cl2) Materials (total 20 mL). After drying the combined organics over 2,5-Diphenyltellurophene (1) and a tellurophene-2,5-
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