Supplementary Data for
Synthesis of New Silica Gel Adsorbent Anchored with Macrocyclic Receptors for Specific Recognition of Cesium Cation
Yuxiao Leng ab, Gang Ye b[*], Jian Xu a, Jichao Wei b, Jianchen Wang a and Jing Chena
a Faculty of Chemical Science and Engineering, China University of Petroleum, Beijing, P. R. China
b Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing, P. R. China
Figure S1. 1H NMR spectra of 1,3-di(2-propoxy)calix[4]arene-crown-6 and the derivatives. For the 1,3-alternate calix[4]arene-crown-6 molecule, the resonances at 7.03 ppm, 6.99 ppm and 6.75 ppm correspond to the chemical shift of the protons in the benzene ring. The methylene groups in the crown unit show signals at 3.59 ppm, 3.55 ppm, 3.46 ppm, 3.31 ppm and 3.11 ppm. The chemical shift of 4.20 ppm and 0.82 ppm are assigned to the different protons in the isopropyl. After the selective nitration reaction, the resonance of the protons in 1,3-alternate benzene rings shifts to the low field (8.03 ppm) due to the electron withdrawing ability of the nitro groups. In the meantime, the chemical shift of the protons in the isopropyl shows the same tendency. However, the protons in the unsubstituted benzene rings have no obvious change. For the NH2-calix[4]arene-crown-6 (3), the nitro substituents are transformed to amino groups ,which have a electron donating effect to the benzene rings. Accordingly, the proton at the ortho- position of the amino shows resonance at 6.55 ppm.
Figure S2. 13C NMR spectra of 1,3-di(2-propoxy)calix[4]arene-crown-6 and the derivatives. The peaks at 156.9 ppm, 154.8 ppm, 134.5 ppm, 133.7 ppm, 130.2 ppm and 121.9 ppm are the resonances of the carbon in benzene rings. The two peaks of the carbon atoms emerged at the low field are attributed to the carbons connecting to oxygen atoms. The carbon in the crown ring shows resonance at about 70 ppm. The signals at 72.7 ppm and 22.0 ppm correspond to the carbon atoms in the isopropyl group. After the nitration reaction, the effect of the nitro groups can be observed in the 13C NMR spectra. The carbon atom adjacent to the nitro group shifted from 121.9 ppm to 141.9 ppm due to the electron withdrawing effect. For the reduction product (3), the electron donating ability of the amino groups resulted in a tendency of chemical shift to high field for the carbon atoms in the benzenes.
Figure S3. FT-IR spectra of 1,3-di(2-propoxy)calix[4]arene-crown-6. IR (KBr) (ν, cm-1): 3057.8, 3011.7, 2965.6, 2868.3, 1613.7, 1583.0, 1454.9, 1373.0, 1214.2, 1116.9.
Figure S4. FT-IR spectra of NO2-calix[4]arene-crown-6 (2). IR (KBr) (ν, cm-1): 3072.7, 2965.1, 2919.0, 2867.8, 1607.9, 1582.3, 1517.7, 1454.3, 1331.3, 1223.8, 1095.7.
Figure S5. FT-IR spectra of NH2-calix[4]arene-crown-6 (3). IR (KBr) (ν, cm-1): 3420.9, 3349.3, 3072.9, 3026.6, 2970.3, 2893.4, 2857.6, 1602.8, 1485.0, 1449.1, 1354.3, 1244.3, 1203.3, 1100.9.
Figure S6. N2 adsorption-desorption isotherms of the precursor and the calix-grafted product.
Figure S7. Large-scale ESEM micrograph of the organosilica particles
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[*] Corresponding author: e-mail, .