Gemini guests with spacers of various length drive the self-assembling of supramolecular capsules in water at neutral pH differently

Article abstract of DOI:10.1080/10610278.2013.826806

Water-soluble homodimeric capsules resulting from the electrostatic and hydrophobic interactions between a tetracationic calixarene receptor and gemini guests having the negatively charged ends separated by a (-CH₂-) _n (n = 2-6) spac

Full text of DOI:10.1080/10610278.2013.826806

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Gemini guests with spacers of various length drive the
self-assembling of supramolecular capsules in water at
neutral pH differently
Carmelo Sgarlataa, Giuseppe Arenaa, Domenico Sciottoa & Carmela Bonaccorsoa
a Dipartimento di Scienze Chimiche, Università degli Studi di Catania, Viale A. Doria 6,
95125Catania, Italy
Published online: 25 Aug 2013.
To cite this article: Carmelo Sgarlata, Giuseppe Arena, Domenico Sciotto & Carmela Bonaccorso (2013) Gemini guests
with spacers of various length drive the self-assembling of supramolecular capsules in water at neutral pH differently,
Supramolecular Chemistry, 25:9-11, 696-702, DOI: 10.1080/10610278.2013.826806
To link to this article: http://dx.doi.org/10.1080/10610278.2013.826806
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Supramolecular Chemistry, 2 01 3
Vo l . 2 5 , N o s . 9 – 1 1 , 6 96 – 7 02 , h t t p: / / d x. d o i . or g / 1 0. 1 0 8 0 / 10 6 1 0 2 7 8 . 2 01 3. 8 2 68 0 6
Gemini guests with spacers of various length drive the self-assembling of supramolecular
capsules in water at neutral pH differently
Carmelo Sgarlata, Giuseppe Arena, Domenico Sciotto and Carmela Bonaccorso*
`
Dipartimento di Scienze Chimiche, Universita degli Studi di Catania, Viale A. Doria 6, 95125 Catania, Italy
(Received 22 May 2013; final version received 10 July 2013
)
Water-soluble homodimeric capsules resulting from the electrostatic and hydrophobic interactions between a tetracationic
a
calixarene receptor and gemini guests having the negatively charged ends separated by a (ZCH2Z)n (n ¼
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Keywords: calixarenes; gemini guest; supramolecular capsules; water chemistry; self-assembly
1. Introduction
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Non-covalent, weak interactions have been widely
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gemini guests of variable size (BSCn, n ¼
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Anionic components able to drive the self-assembly of
o
2. Results and discussion
The dianionic guests BSCn (n ¼
molecules have been recently used in supramolecular
chemistry to obtain non-covalently linked molecular
3
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–
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With the aim of building up supramolecular anion
p
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( 10
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.
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n t
n n
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B
C
receptors by using simple building blocks, we resorted to
p
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y
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w
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i
s
2
,
2
4
*Corresponding author. Email: bonaccorsoc@gmail.com
q 2013 Taylor & Francis

Supramolecular Chemistry
697
Scheme 2. Synthesis of the BSCn
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.
Scheme 1. The investigated host and guest.
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i
s
r
e
v
e
r
s
i
b
l
y
b
o
u
n
d
t
o
t
h
e
h
h
o
s
t
;
e
e
m
o
r
e
o
v
e
r
,
t
h
e
a
d
h
o
c e
d BSCn
t
a
i
l
o
r
d
f
u
n
c
t
i
o
n
a
l
i
s
a
t
i
o
n
o
f
b
o
t
t
h
h
a
n
d
6
)
o
r
w
i
t
h
C
l
S
O
H
(
f
o
r
n
¼
4
a
n
d
5
)
.
A
l
l
t
h
e
c
a
l
i
x
a
r
e
n
i
c
c
a
v
i
t
y
a
n
a
l
l
o
w
s
f
o
r
t
r ie n t a t i o n a n d l o c a t i o n o f e n c a p s u l a t e d g u e s ts .
h
e
c
o
n
t
r
o
l
o
f
t
3
i
n
t
e
r
m
e
d
i
a
t
1 3
e
s
a
n
d
fi
n
a
l
c
s
o
m
p
o
u
n
d
s
w
e
r
e
c
h
a
r
a
c
t
e
r
i
s
e
d
b
y
o
1
H
a
r
n
d
C
N
M
R
p
e
c
t
r
o
s
c
o
p
i
e
s
a
n
d
E
S
I
m
a
s
s
The refinement of the NMR titration data yields the
e
s
p
e
c
t
o
m
e
t
r
y
(
s
e
e
S
u
p
p
l
e
m
e
n
t
a
r
y
I
n
f
o
r
m
a
t
i
o
n
,
a
v
a
i
l
a
b
l
e
binding constants for the different BSCn– TAC4
s
y
s
t
m
s
o
n
l
t
i
n
e
)
(
S
c
h
e
m
e
2
)
.
i
n
b
u
f
f
e
r
e
d
D
O
(
p
D
7
s
.
1
)
a
t
2
7 8
d
C
( 12
y
)
.
A
g
o
o
d
fi
t
o
f
t
h
e
e
h
n
2
Standard 1H NMR titrations (11
)
w
e
r
e
c
a
r
r
i
e
d
a
o
u
t
t
o
e
n
e
x
p
e
r
i
m
e
n
t
a
l
d
a
t
a
w
a
o
b
t
a
i
n
e
o
n
l
b
y
c
o
n
s
i
d
e
r
i
n
g
t
h
d
b
e
e
r
m
i
n
e
e
a
n
b
o
t
h
t
h
e
s
t
e
r
e
o
c
h
e
m
i
s
t
r
y
o
f
i
n
c
l
u
s
i
o
n
n
d
t
h
i
s
i
m
u
l
t
a
n
e
o
u
s
f
o
r
m
a
t
i
o
n
o
f
c
o
m
p
l
e
x
s
p
e
c
i
e
s
h
a
v
i
n
g
b
o
t
i
n
d
i
n
g
f
fi
n
i
t
i
e
s
o
f
B
S
C
n
(
n
¼
3
–
e
5
)
f
o
r TAC4
g
1
:
1
a
n
d
2
:
1
h
o
g b
s
t
–
g
u
e
s
t
s
t
o
i
c
h
i
o
m
e
t
r
y
.
T
h
e
a
s
s
o
c
i
a
t
i
o
w
a
t
e
r
a
e
t
e
a
u
t
r
a
l
p
H
.
D
u
e
t
o
t
h
e
f
a
s
t
x
c
h
a
n
e
b
e
s
e
t
w
e
e
n
c
e
o
n
s
t
a
n
t
s
(
l
o
)
f
o
r
t
h
e
s
e
s
p
e
c
i
e
s
,
t
h
e
a
h
o
s
t
–
g
u
e
s
t
t
t
h
e
f
r
n
d
t
h
e
c
o
m
p
l
e
x
e
d
s
p
e
c
i
e
s
o
n
t
h
N
M
g
R
q
u
i
l
i
b
r
i
a
a
n
d
t
h
e
d
i
s
t
r
i
b
u
t
i
o
n
d
i
a
g
r
a
m
s
r
e
s
h
o
w
n
i
n
i
m
e
s
c
a
a
l
e
,
t
h
W
e
g
u
e
s
t
s
i
g
n
a
l
s
w
e
r
e
d
e
t
e
c
t
e
d
a
s
i
n
l
e
T
a
b
l s
The species distribution diagrams indicate that BSC4
e
1
a
n
d
F
i
g
u
r
e
s
2
a
n
d
3
,
r
e
p
e
c
t
i
v
e
l
y
.
r
e
s
o
n
g
n
c
e
s
.
h
e
n
t
h
e
h
o
s
t
c
o
n
c
e
n
t
r
a
t
i
o
n
i
n
c
r
e
a
e
s
e
s
,
a
l
l
t
h
e
d
u
e
s
t
s
i
g
n
s
a
l
s
s
h
i
f
t
u
p
fi
e
l
d
a
n
d
t
h
e
c
o
m
p
l
x
a
t
H q
i
o
n
-
f
o
r
m
s
a
s
u
p
r
a
m
o
l
e
c
u
l
a
r
c
a
p
s
u
l
e
(
i
.
e
.
b
o
t
h
H
G
a
n
d
H
G
2
i
n
u
c
e
d
s
h
i
f
t
(
C
I
S
)
f
o
l
l
o
w
t
h
e
o
r
d
e
r
M
e
.
A
r
s
p
e
c
i
e
s
a
r
e
s
u
c
c
e
s
s
f
u
l
l
y
r
e
fi
n
e
d
)
w
i
t
h
a
s
r BSC2 a nd BSC6 (10) whi le BSC5
t
a
b
i
l
i
t
y
c
o
m
p
a
r
a
b
l
e
C
H
(
F
i
g
u
r
e
1
)
.
T
h
e
t
r
e
n
d
r
e
p
o
r
t
e
d
i
n e
s BSC2–TAC4
F
i
g
u
r
1
h
a
s
t
o
t
h
a
t
o
b
s
e
r
v
e
d
f
o
2
a
a
l
r e
d BSC6–TAC4
a
d
y
b
e
e
n
o
b
s
e
r
v f
s y s t e m s ( 10) .
e
d
o
r
t
h
e
a
n
a
l
o
g
o
u
a
BSC3
s
s
e
m
b
l
e
s
i
n
t
o
a
l
e
s
s
s
t
a
b
l
e
c
a
p
s
u
l
a
r
e
n
t
i
t
y
.
S
u
r
p
r
i
s
i
n
g
l
y
,
n
s
e
e
m
s
p
o
o
r
l
y
s
u
i
t
a
b
l
e
f
o
r
c
a
p
s
u
l
e
f
o
r
m
a
t
i
o
n
;
t
h
e
H
G
The selective inclusion of the aromatic moiety of the
s
p
e
c
i
e
s
i
s
b
y
f
a
r
t
h
e
m
o
s
t
r
e
l
e
v
a
n
t
i
n
t
The formation of the homodimeric structure does not
h
i
s
s
y
s
t
e
m
.
guest is supported by the large upfield shift of both the
signals of the methyl groups and the two neighbouring
aromatic protons, indicating that the above groups are
included into the host cavity and experience the magnetic
imply any stabilising linkage between the two
calixarenic scaffolds; concerted electrostatic and hydro-
phobic interactions between TAC4
a
n
d
t
h
e
g
u
e
s
t
s
a
r
e
t
h
e
shielding of the aromatic rings of TAC4. S u c h a n
e
a
a
t
t
r
a
c
t
i
v
e
f
o
r
c
e
s
h
o
l
d
i
n
g
t
o
g
e
t
h
e
r
t
h
e
s
u
p
n
r
a
m
o
n u m b e r o
l
e
c
u
l
a
r
f
a
r
r
a
n
g
e
m
e
n
t
m
a
x
i
m
i
s
e
s
t
h
C
H
– p
a
a
n
d p– p
m
i
n
t
e
r
a
c
t
i
o
n
s
s
s
e
m
b
l
i
e
s
.
H
o
w
e
v
e
r
,
t
h
e
d
i
f
f
e
r
e
n
t
l
e
n
g
t
h
a
d
g
b
e
t
w
e
e
n
t
h
e
h
o
s
t
a
n
d
t
h
e
g
f BSCn
u
e
s
t
n
d
s
o
e
w
h
a
t
k
e
e
p
s
t
h
u e o u s
e
m
e
t
h
y
l
e
n
e
g
r
o
u
p
e
s
f
o
n
t
h
e
a
l
k
y
f
l
c
h
a
i
n
o
f
t
h
e
u
e
s
t
s
s
e
e
m
l
i
p
o
p
h
i
l
i
c
m
o
i
e
t
i
e
s
o
a
w
a
y
f
r
o
m
t
h
e
p
o
l
a
r
a
q
t
o
a
f
f
e
c
t
t
h
e
fi
c
i
e
n
c
y
o
t
h
e
c
a
p
s
u
l
e
t
e
m
p
l
a
t
i
o
n
e
n
v
i
r
o
n
m
e
n
t
.
s
t
N
e
g
l
i
g
i
b
l
e
s
h
i
f
t
s
a
r
e
o
b
s
e
r
v
e
d
f
o
r
t
h
e
o
s
t
h
e
r
p
r
o
c
e
s
s
The assemblies with an odd number of CH2 units are less
.
g
u
e
s
t
s
i
g
n
a
l
s
u
g
g
e
s
t
i
n
g
f
t
h
a
t
t
h
e
s
u
l
p
h
o
n
a
t
e
g
r
o
u
p
a
r
e
l
t
o
c
a
t
e
d
n
e
a
r
h
e
c
p
o
r
t
a
l
o
t
h
e
h
o
s
t
,
t
o
t
a
k
e
f
u
l
l
a
d
v
a
n
t
a
g
e
o
f
stable than BSC4
a
,
p
o
r o b a b l y ow i n g t o a n u ns u it a bl e
s
h
e
e
l
e
c
t
r
o
s
t
a
t
i
i
n
t
e
r
a
c
t
i
o
n
s
w
i
t
h
t
h
e
a
m
m
o
n
i
u
m
g
r
o
u
p
s
a
t
r
r
a
n
g
e
m
e
n
t
o
f
t
h
e
t
w
c
a
l
i
x
a
r
e
n
i
c
c
a
f
f
o
l
d
s
a
r
o
u
n
d
B
S
C
3

698
C. Sgarlata e t a l .
a
Table 1. Binding constants (log b
O
)
f
C
o
r
.
t
h
e BSCn– TAC4
log b2
s
y
s
t
e
m
s
(
n
¼
2
–
6
)
i
n
D
2
a
t
p
D
7
.
1
,
2
7
8
Guest
log b1
4.54
BSC2b
BSC3
BSC4
BSC5
BSC6c
7.85
4.22 (1)
4.52 (3)
4.45 (3)
4.34
6.43 (2)
7.69 (3)
7.20 (3)
7.40
a s
b From Ref. (10b
c From Ref. (10a
i
n
p
a
r
e
n
t
h
e
s
e
s
.
)
.
)
.
(
7
.
2
0
v
s
.
6
.
4
3
)
,
t
h
o
u
g
h
t
h
e BSC5
e BSCn (n ¼
Diffusion-ordered NMR spectroscopy (DOSY) pro-
vides further evidence that supports the unexpected
a
s
s
e
m
b
l
y
i
s
l
e
s
s
s
t
a
b
l
e
t
h
a
n
t
h
o
s
e
f
o
r
m
e
d
b
y
t
h
2
,
4
,
6
)
h
o
m
o
l
o
g
u
e
s
.
behaviour of the BSC3– TAC4
s
y
s
t
e
m
.
A
s
t
t
h
e
f
r
e
e
a
n
d
b
o
o
b
u
n
d
g
u
e
s
t
e
x
c
h
a
n
g
e
f
a
s
t
o
n
t
h
e
N
M
R
i
m
e
s
c
a
l
e
,
t
h
e
s
e
r
v
e
d
d
s
i
f
f
u
s
i
o
n
c
o
e
f
fi
c
i
e
n
t
s
a
r
e
t
h
e
w
e
i
g
h
t
e
d
a
v
e
r
a
g
e
o
f
f
t
i
h
e
v
a
l
u
e
o
f
t
h
e
f
r
e
e n
f TAC4
a
d
b
o
u
n
d
g
u
e
s
t
.
T
h
e
a
d
d
i
t
i
o
n
o
n
c
r
e
a
s
i
n
g
a
m
o
u
n
t
s
o
a
f
f
e
c
t
s
t
h
e
m
o
t
e TAC4
i
o
n
o
f BSC3
i
w
h
i
l
e
i
t
c
a
u
s
e
s
a
e
s
m
a
l
l
e
f
f
e
c
t
o
i
n
t
h
d
i
f
f
u
s
o
n
c
o
e
f
fi
c
i
e
n
t
(
F
i
g
u
r
5
)
;
t
h
e
g
u
e
s
t
d
f
f
u
s
e
s
m
o
r
e
s
l
o
w
l
y
t
h
a
n
i
n
i
t
s
f
r
e
e
f
o
r
m
,
w
h
i
c
h
i
s
c
o
n
s
i
s
t
e
n
t
w
i
t
h
a
n
i
n
c
(13
r
e
a
s
e
o
f
i
t
s
e
f
f
e
c
t
i
v
e
s
i
z
e
d
u
e
t
o
h
o
s
t
–
g
u
e
s
t
i
n
t
e
r
a
c
t
i
o
n
s
)
.
Only the model (HG þ H2G) nicely fits the exper-
imental self-diffusion coefficients, thus pointing out that
the two species coexist in neutral solution. However, both
NMR titration and DOSY data indicate that the amount of
(TAC4)
( ,
–
B
S
C
3
a
s
s
e
m
b
l
y
f
o
r
m
i
n
g
n
i
n
s
o
l
u
t
i
o
n
i
s
r
e
l
a
t
i
v
e
l
y
2
s
m
a
l
l
3
f TAC4
0
%
,
F
i
g
u
r
e
3
(
a
)
)
e
v
e
n
i
t
t
h
e
p
r
e
s
e
n
c
e
o
f
a
l
a
r
g
e
e
x
c
e
s
s
o
n
(
F
i
g
u
r
e
5
)
.
M
o
s
o
e
f
t
h
e
e
x
p
e
r
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x
p
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t
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f
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r
1
:
1
s
p
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i
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(
b
l
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)
,
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u
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G
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m
a
i
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p
e
c
i
e
s
i
n
s
o
l
u
t
i
o
n
.
The diffusion coefficients extrapolated from the exper-
imental data (De x
, T a b l e 2 ) fo r t h e HG an d H G co m p l exe s
2
t
r
1
0
2
1
1 0
02
2
1
s2
(
3
.
0
5
£
1
0 2
m
s2
a
n
d
2
.
5
2
£
1
m
,
( DT
r
e
s
p
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c
t
i
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y
)
a
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l
02
o
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e
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2
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1
h
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o
f
t
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f
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o
m
p
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t
s
¼
3
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1
0
A
C
4
1
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2
1
0
2
1
£
1
m
s
,
D
¼
4
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0
4
£
1
0 2
m
s2
)
a
n
d
n
i
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y
B
S
C
3
m
a
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c
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t
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i
c
a
l
v
a
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(
D
)
.
c
a
l
c
d
The diffusion coefficient extrapolated for (TAC4
e
)
–
2
BSC3
i
s
s
y BSC2 (10b
o
m
e
w
h
a
t
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o
m
p
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r
a
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b
)
y BSC6 ( 10a
a
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fi
c
o
p
a
n
t
l
y
l
a
r
g
e
r
t
h
a
n
t
h
a
Figure 1. (Colour online) CIS diagrams for the BSCn– TAC4
b
)
,
w
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h
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o
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p
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p
a
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7
y
s
,
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e
2
m
78
s
C
(
n
¼
3
. CBSCn
,
4
,
¼
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f
2
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r
(
a
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1
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(
b
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)
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2
,
p
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a
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a
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a
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s
e
m
b
l
y
.
T
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fi
n
d
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3
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5
£
02
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b
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d
s
t
r
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t
u
r
e
i
n
v
o
l
v
i
n
s e r v e d f o r t h e s e r i es o f
g
B
S
C
3
,
a
l
t
h
o
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t
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(
F
i
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r
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4
)
.
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b
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h
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l
k
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p
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h
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e
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r
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o
f
c
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f
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m
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t
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d
o
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k
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p
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o
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d
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g
a
t
i
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f
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S
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a
t
l
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d
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t
f
r
o
m
t
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p
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f
t
h
u
3. Conclusions
h
o
o
s
t
,
w
h
i
c
h
w
o
u
l
d
d
e
t
e
r
m
i
n
e
h
e
s
l
i
g
h
t
l
y
l
o
w
e
r
v
a
l
b
s
e
r
v
e
d
a
l
s
o
f
o
r
t
h
e
fi
e BSC5
r
s
t
e
q
u
i
l
i
c
c
b
r
i
u
m
.
T
h
e
r
e
l
a
t
i
v
e
l
y
l
o
n
g
e
r
r
r
Dianionic gemini guests having different size can be
successfully used as templating agents for the assembly of
nanoscale homodimeric capsules in aqueous solution at
a
n
d
m
o
r
e
fl
e
x
i
b
l
a
l
k
y
l
i
c
h
a
i
n
p
a
r
t
i
a
l
l
y
a
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r
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t
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r
e
w
i
t
h
t
h
e
l
o
n
g
e
r
s
p
a
c
e

Supramolecular Chemistry
699
Figure 2. (Colour online) Schematic of the host–guest equilibria for the TAC4 – BSCn s y s t e m s .
neutral pH. Capsules are formed by concerted hydro-
phobic and electrostatic interactions between the aromatic
NMR titrations were carried out by mixing BSCn
d TAC4 i n t h e a p pr o pr i a te r a t io s i n N M R t ube s
a
n
and charged moieties at both ends of the BSCn
t
g
u
e
s
t
s
a
n
d
i
n
D
O
m
(BSCn
3
c
o
n
c
e
n
t
r
a
t
i
o
n
w
a
s
k
e
p
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t
a
n
t
a
t
2
.
5
£
2
4
2
3
h
e
t
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a
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i
o
n
i
c
c
a
l
i
x
[
4
]
a
r
e
n
e
h
o
s
t
DOSY experiments and the accurate determination of
.
1
02
o
l
d
m2
;
p
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o
s
p
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a
t
e
b
u
f
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r
2
.
5
£
1
m
o
l
d
)
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T
h
e
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c
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l
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f
t
s
c
o
r
r
e
s
p
o
n
d
i
n
g
t
o
a
l
l BSCn
s
r
e
s
o
n
a
n
c
e
s
the species existing in solution reveal that the amount of
dimeric capsule that forms strongly depends on the
number of methylene groups on the alkyl chain of the
guest. This paves the way to new strategies for the design
of more efficient supramolecular containers that could be
used as molecular reactors or shuttles for the delivery of
biologically relevant molecules. Isothermal titration
calorimetry measurements and theoretical calculations
are currently underway to single out the forces that drive
the capsule formation processes.
c
o
l
l
e
c
t
e
d
i
n
t
h
e
1
–
8
h
o t
(12
s
–
g
u
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t
r
a
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fi
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u
s
i
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g
H
y
p
e
r
N
M
R
)
;
t
h
e
a
b
o
v
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a
t
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n
s
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t
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a
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t
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a
m
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p
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m
2
0
%
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%
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f
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a
l
g
u
e
s
t
c
o
n
c
e
n
t
r
a
t
i
o
n
.
NMR diffusion measurements were carried out using
the bipolar-pulsed gradient-stimulated echo (due to the
long eddy-current delay) Varian pulse sequences (16
)
a
n
d
w
e
r
e
p
n
r
o
c
e
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d
b
y
t
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V
a
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a
n
D
O
S
Y
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w
a
r
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i
n
c
o
r
p
o
r
-
a
t
e
d
i
V
N
M
R
.
Data were acquired with a 75 ms diffusion delay in all
experiments, with a bipolar gradient pulse duration of
2 ms. For all experiments, 25 different gradient amplitudes
were used, until a 90% decrease in the resonance intensity
4. Experimental
was achieved. A constant concentration of BSCn
3
m 2
)
w
0
a
s
u
s
e
d
w
h
i
l
e
t
h e c o n c e n t r at i o n o f
3
4.1 General
(
0
TAC4
.
2
5
m
m
o
l
d
TAC4
w
a
s
o
b
t
a
i
n
e
d
( 14
a
c
c
o
r
d
i
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g
c
t
o
t
h
e
p
r
o
c
e
d
u
r
e
f BSCn
d
e
s
c
r
i
b
e
d
r
a
n
g
e
d
f
r
o
m
.
2
5
t
o
2
.
5
0
m
m
o
l
d
.
b
TAC4
y
G
u
t
s
c
h
e
e
t
a
l
.
)
.
T
h
o
e
o
n
c
e
n
t
r
a
t
i
o
n
o
a
n
d
The diffusion coefficients were obtained by the
following equation:
w
a
s
o
b
t
a
i
n
e
d
b
y
c
r
r
e
c
t
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a
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o
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t
e
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d
v
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a
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G
A
.
A
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� �
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2
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(
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,
M
O
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U
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A
)
a
n
d
u
s
d
a
s
s
I
2
D 2 d
l
n
¼ 2g2 d2 G2
D ¼ 2b D;
e
c
e
i
v
e
d
,
a
f
t
e
r
d
r
y
i
n
g
.
T
h
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l
a
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e
r
c
h
r
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a
t
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r
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p
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w
a
I0
p
4
c
a
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d
o
u
t
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n
s
i
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c
a
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e
l
p
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a
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s
(
M
e
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c
k
6
0
,
F
2
5
4
,
M
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r
c
k
,
D
a
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s
t
a
d
t
,
G
e
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m
a
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y
)
.
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a
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r
where I
a
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d I0
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p
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, G
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(
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, d
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(15
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, D
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t
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p ul s e
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t
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w
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)
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o
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t w
d D
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a
d
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t
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c
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f
fi
c
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e
n
t
.
4.2 NMR experiments
NMR experiments were carried out at 278C using a
500 MHz spectrometer (1H NMR at 499.88MHz, 13C NMR
at 125.7 MHz) equipped with a pulse field gradient module
4.3 Synthesis
4.3.1 General procedure for the synthesis of BCn
(Z
-
a
x
i
s
)
a
n
d
c
t
a
t
u
n
a
b
l
e
5
m
m
V
a
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d
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t
e
c
t
i
o
n
p
nd a r
r
o
b
e
Terminal dibromoalkane (5.0 mmol) was added to a stirred
suspension of 4-methyl-phenol (1.04 ml, 10.0 mmol) and
K2CO3 (1.38 g, 10.0 mmol) in acetonitrile (50 ml). The
mixture was refluxed overnight and then allowed to cool
(
r
I
D
-
P
F
G
)
;
h
e
m
i
c
a
l
s
h
i
f
t
s
(
d
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a
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x
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a
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d s
es tR eC s of tware.
e
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.
N
M
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d
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a s s e m b l y.
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3

Supramolecular Chemistry
Supporting Information
701
Table 2. Self-diffusion coefficients for the BSC3–TAC4
C
Supplementary information (available online): 1H and 13
NMR spectra of BCn and BSCn.
C
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BSC3
TAC4
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4.04
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4.04 (2)
3.10 (1)
3.05 (2)
2.52 (2)
Acknowledgements
University of Catania (Progetto d’Ateneo) and MIUR (Firb
MERIT RBNE08HWLZ) are gratefully thanked for partial
support.
TAC4:BSC3 (1:1) 1070
TAC42:BSC3 (2:1) 1726
a s
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/
z
:
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0
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.
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e
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o
u
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–
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2
9
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.
9
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A
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