Supporting Information Synthesis of a hexacationic cyclophane and formation of EDA-type host-guest complexes Journal of Inclusion Phenomena and Macrocyclic Chemistry Hiroyuki Takemura*, Saori Nakata, Akiko Inoue, and Ayaka Mishima Department of Chemical and Biological Science, Faculty of Science, Japan Women’s University, Mejirodai 2-8-1, Bunkyou-ku, Tokyo 112-8681, Japan Corresponding author. E-mail: takemurah@fc.jwu.ac.jp 1 Contents 1.1 1.2 1.3 1.4 UV titration experiment Job plots Fluorescent titration experiment Component ratio determination ~ Fluorescent titration 2.1 2.2 1 H NMR spectrum of polycationic cyclophane 3. 13 C NMR spectrum of polycationic cyclophane 3. 2 General procedure Absorption spectra were recorded on SHIMADZU MultiSpec-1500 UV-VIS spectrophotometer. Fluorescent spectra were recorded on JASCO FP-750 spectrofluorometer. 1.1 UV titration experiment Aliquot solutions (CH3CN) of the calixresorcin[4]arene (1.02×10-2 mol/L) was added to a solution of the cyclophanes 3b (1.00×10-3 mol/L). The cyclophane solutions (1.00 mL) and 0 ~ 9 mL of the guest solutions were mixed in volumetric flask and diluted to 10.00 mL with CH3CN. Separately, a solution of the guest (1×10-2 mol/L) was prepared. The UV spectra of the solutions were recorded in the range of 350~600 nm. The absorption of the CT band at 420 nm was measured. Figure UV/vis titration spectra. 3 Figure Titration curve and nonlinear fitting. Analysis: In the 1 : 1 host-guest system, Aobs =Aobs – A0 can be written by the equation below. Aobs = b11/2K11[1+ K11[H]0 + K11[G]0 – {(1+K11[H]0 + K11[G]0)2 – 4K112[H]0[G]0}1/2] …equation (1) Here, b = cell length 11 = 11 – G, 11; molar absorption coefficient of the complex, G; molar absorption coefficient of the free guest. [H]0 = initial concentration of the host. [G]0 = initial concentration of the guest. K11 = binding constant of 1 : 1 complexation. 4 In our experiments, [H]0 = constant (1.00×103 mol/L). Curve fitting of the equation (1) was achieved by “Kaleida Graph®” software. 1.2 Job plots Solutions of calixresorcin[4]arene (1.0 ×10-2 mol/L, CH3CN, 0 ~ 10 mL) and the cyclophanes 3b (1.0 ×10-2 mol/L, 10 ~ 0 mL) was mixed in volumetric flasks. The UV spectra of the solutions were recorded in the range of 350~600 nm. The absorption of the CT band at 420 nm was measured. Total concentration of the host and the guest were preserved as constant (0.20×10-2 mol/L). 5 1.3 Fluorescent titration experiment Aliquot solutions (CH3CN) of the cyclophanes 3b (2.07×10-5 mol/L and 1.04×10-3 mol/L). was added to a solution of pyrene (2.28×10-4 mol/L). The pyrene solutions (1.00 mL) and of the host solutions (2.07×10-5 mol/L; 0.00, 1.00, 2.00, and 4.00 mL: 1.04×10-3 mol/L; 0.2, 0.4, 0.8, 2.0, 4.0, and 8.0 mL) were mixed in volumetric flask and diluted to 10.00 mL with CH3CN. The fluorescent spectra of the solutions were recorded in the range of 350~550 nm, (excitation, 343 nm). The intensity at 393 nm was measured. Figure Fluorescent titration spectra. 6 Figure Fluorescent titration curve. 1.4 Component ratio determination ~ Fluorescent titration An Aliquot of the stock solutions of the cyclophanes (1.02 × 10-4 mol/L) and pyrene (2.28 × 10-4 mol/L) were mixed. The fluorescent spectra of the solutions were recorded in the range of 350~550 nm, excitation, 343 nm). The intensity at 393 nm was measured. 7 8 2.1 9 2.2 10