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:

Contents

1.1UV titration experiment

1.2Job plots

1.3Fluorescent titration experiment

1.4Component ratio determination ~ Fluorescent titration

2.11H NMR spectrum of polycationic cyclophane 3.

2.213C NMR spectrum of polycationic cyclophane 3.

General procedure

Absorption spectra were recorded on SHIMADZU MultiSpec-1500 UV-VIS spectrophotometer. Fluorescent spectrawere recorded on JASCO FP-750 spectrofluorometer.

1.1 UVtitration experiment

Aliquot solutions (CH3CN) of the calixresorcin[4]arene (1.02×10－2 mol/L) was added to a solution of the cyclophanes3b (1.00×10－3mol/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 420nm was measured.

Figure UV/vis titration spectra.

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 = b11/2K11[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.

In our experiments, [H]0 = constant (1.00×103 mol/L).

Curve fitting of the equation (1) was achieved by “Kaleida Graph®” software.

1.2Job plots

Solutions of calixresorcin[4]arene (1.0 ×10－2 mol/L, CH3CN, 0 ~ 10 mL) and the cyclophanes3b (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 420nm was measured. Total concentration of the host and the guest were preserved as constant (0.20×10－2mol/L).

1.3Fluorescent titration experiment

Aliquot solutions (CH3CN) of the cyclophanes3b (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.

Figure Fluorescent titration curve.

1.4Component 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.

2.1


2.2

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