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
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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.
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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 = 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.
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In our experiments, [H]0 = constant (1.00×103 mol/L).
Curve fitting of the equation (1) was achieved by “Kaleida Graph®” software.
1.2 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).
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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.
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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.
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8
2.1
9
2.2
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