Electronic Supplementary Information (ESI) Fluorescence-Switchable Luminogen in Solid State: A Sensitive and Selective Sensor for the Fast Turn-On Detection of Primary Amine Gas Tianyu Han, ab Jacky W. Y. Lam, a Na Zhao, a Meng Gao, a Zhiyong Yang, a Engui Zhao, a Yuping Dong *b and Ben Zhong Tang *acd a Department of Chemistry, Institute for Advanced Study, State Key Laboratory of Molecular Neuroscience, Institute of Molecular Functional Materials and Division of Biomedical Engineering, The Hong Kong University of Science & Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong, China. E-mail: tangbenz@ust.hk b College of Materials Science and Engineering, Beijing Institute of Technology, 5 South Zhongguancun Street, Beijing, 100081, China. E-mail: chdongyp@bit.edu.cn; fax: +86-10-6894-8982 c Guangdong Innovative Research Team, SCUT-HKUST Joint Research Laboratory, State Key Laboratory of Luminescent Materials and Device, South China University of Technology (SCUT), Guangzhou 510640, China. d HKUST Shenzhen Research Institute, No. 9 Yuexing 1 st RD, South Area, Hi-tech Park, Nanshan, Shenzhen, China 518057. Experimental section Materials and Instrumentations Tetrahydrofuran (THF) and ethanol were distilled from sodium benzophenone ketyl and magnesium, respectively, under nitrogen immediately prior to use. Other chemicals were purchased from Aldrich and Alfa Aesar and used as received without further purification. 1 H spectra were measured on a Bruker AV 400 spectrometer in dimethylsulfoxide (DMSO) using tetramethylsilane (TMS; δ = 0) as internal reference. 1
High resolution mass spectra (HRMS) were recorded on a GCT premier CAB048 mass spectrometer operated in MALDI-TOF mode. UV spectra were measured on a Milton Roy Spectronic 3000 Array spectrophotometer. Photoluminescence (PL) spectra were recorded on a Perkin-Elmer LS 55 spectrofluorometer. The PL quantum yields (Φ F ) of TPPA in THF and THF/water mixtures were determined using quinine sulfate (Φ FL = 54% in 0.1 M sulfuric acid solution) as standard. The morphologies of the nanofibres of TPPA were investigated using JOEL 2010 Transmission Electron Microscopy (TEM). Powder X-ray diffraction (XRD) patterns were recorded on an X'pert PRO, PANalytical diffractometer. The ground-state geometries were optimized using the density functional (DFT) with B3LYP hybrid functional at the basis set level of 6-31G. All the calculations were performed using Gaussian 03 package. Synthesis 4-(2,5-diphenyl-1-pyrrolyl)benzoic acid (TPPA) was prepared according to the synthetic route shown in Scheme S1. Details can be found in our previous publications. 1,2 Its 1 HNMR and mass data are given below. 1 H NMR (400 MHz, DMSO-d 6 ), δ (TMS, ppm): 13.15 (s, 1H), 7.86 7.84 (d, J = 8.4 Hz), 7.24 7.16 (m, 8H), 7.05 7.03 (d, J = 7.2 Hz), 6.51 (s, 2H). HRMS (MALDI-TOF): m/z 339.1255 [M +, calcd 339.1259]. Scheme S1 Synthetic route to TPPA 2
Fig. S1 1 HNMR spectrum of TPPA. hty-tp2, mw=323; CH4 tan120730_1 65 (1.978) Cm (64:66-(1:53+83:86)) 100 339.1255 TOF MS CI+ 8.75e3 340.1320 % 341.1346 0 191.0859 294.1302 338.1172 368.1658 189.0722 192.0926 217.0885 235.0765 278.0979 322.1252 369.1699 m/z 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 Fig. S2 MALDI-TOF mass spectrum of TPPA. 3
A 1681 B 1625 C 1681 2000 1600 1200 800 Wavenumber (cm - 1 ) Fig. S3 IR spectra of TPPA films (A) before and (B and C) after fumed with (B) butylamine and (C) triethylamine gas. 5 10 15 20 25 30 2θ (deg) Fig. S4 X-raydiffractograms of TPPA drop-casting films (red) before and (black) after exposed to butylamine gas. 4
Untreated film Fumed film Absorbance (au) 250 300 350 400 450 Wavelength (nm) Fig. S5 Absorbtion spectra of TPPA films before (black) and after (red) fumed by butylamine gas. Intens ity (au) Blank BA CHA DA DEA DIPA DMA DOA DPA EA EDA HA HeA PD PDA TEA 360 400 440 480 520 560 600 Wavelength (nm) Fig. S6 Fluorescent photos and emission spectra of TPPA-loaded filter paper strips after dipped into differrent amines. Abbreviation: ethylamine (EA), butylamine (BA), hexylamine (HA), cyclohexylamine (CHA), heptylamine (HeA), ethylenediamine (EDA), propanediamine (PDA), pyridine (PD), dimethylamine (DMA), diethylamine (DEA), dipropylamine (DPA), N,N-diisopropylamine (DIPA), decylamine (DA), di-n-octylamine (DOA) and triethylamine (TEA). Excitation wavelength: 350 nm. The photos were taken under 365 nm UV irradiation from a hand-held UV lamp. 5
References 1 X. Feng, B. Tong, J. B. Shen, J. B. Shi, T. Y. Han, L. Chen, J. G. Zhi, P. Lu, Y. G. Ma and Y. P. Dong, J. Phys. Chem. B, 2010, 114, 16731. 2 T. Y. Han, X. Feng, B. Tong, J. B. Shi, L. Chen, J. G. Zhi and Y. P. Dong, Chem. Commun., 2012, 48, 416. 6