Shielded alkyl-functionalised rotaxane host cavities for improved anion recognition

Article abstract of DOI:10.1080/10610278.2015.1075538

The synthesis and anion recognition properties of four novel [2]rotaxane host architectures containing additional alkyl functionality integrated within macrocyclic and axle components to shield the binding cavity from the solvent are described. The rotaxane species containing a tetra(methyl)-functionalised macrocycle component is found to be a weaker anion complexant than the equivalent unfunctionalised receptor, which is likely due to steric hindrance restricting the anion's access to the interlocked cavity. Rotaxane molecules containing tetra(methyl)-functionalised axle components are also investigated, and the additional alkyl functionality serves to enhance anion binding affinity and selectivity when incorporated within the axle's flexible ethylene linkages. Moreover, the equivalent unfunctionalised rotaxane displays a rare preference for oxoanions over chloride guest species.

Full text of DOI:10.1080/10610278.2015.1075538

Supramolecular Chemistry
ISSN: 1061-0278 (Print) 1029-0478 (Online) Journal homepage: http://www.tandfonline.com/loi/gsch20
Shielded alkyl-functionalised rotaxane host
cavities for improved anion recognition
Lydia C. Gilday, Nicholas G. White & Paul D. Beer
To cite this article: Lydia C. Gilday, Nicholas G. White & Paul D. Beer (2015): Shielded alkyl-
functionalised rotaxane host cavities for improved anion recognition, Supramolecular
Chemistry, DOI: 10.1080/10610278.2015.1075538
To link to this article: http://dx.doi.org/10.1080/10610278.2015.1075538
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Published online: 26 Oct 2015.
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Download by: [Deakin University Library]
Date: 27 October 2015, At: 21:29

Supramolecular Chemistry
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q 2 0 1 5 T a y l o r & F r a n c i s

2
L. C. Gilday
e
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.
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(b)
F
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.

Supramolecular Chemistry
3
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( C o l o u r o n l i n e)
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.
Pseudorotaxane assembly with the novel alkyl-functiona-
f
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w
.
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p
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Synthesis of a novel rotaxane
e
.
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p
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t
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l
(
6
)
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c
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f 8· Cl
e
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8
·
C
l
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h
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m
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2
.
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t 10· Cl ( 3c,7
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(
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)
t
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r
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y
( 5 00 M H z , C D C l , 2 98 K ) .
3

4
L. C. Gilday
e
t
a
l
.
S
c
h
e
m
e
2
.
(
C
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·
C
t
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l
.
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x
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Rotaxane containing an axle-stopper with additional alkyl
functionality
C
r
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d 13· Cl
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Synthesis of a rotaxane containing axle stoppers with
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Rotaxane containing an axle stopper with additional alkyl
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d 15
i
Synthesis of an alkyl-functionalised axle component
.
(
7
)
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·
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6
L. C. Gilday e t a l .
S
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Supramolecular Chemistry
7
S
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Synthesis of a rotaxane containing an alkyl-functionalised
Characterisation of novel rotaxanes
axle with flexible linkages
t
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8
L. C. Gilday e t a l .
Figure 5 (Colour online) 1H NMR spectra of (a) pyridinium chloride axle 10·Cl, (b) [2]rotaxane 11·Cl and (c) macrocycle 9
(500 MHz, CD2Cl2, 298 K).
1
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Supramolecular Chemistry
9
1
Figure 6 (Colour online) H–1H ROESY NMR spectrum of rotaxane 11·Cl. Assignable inter-component through-space interactions
are highlighted (500 MHz, CD2Cl2, 298 K).
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11· PF
t
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n
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Anion recognition properties of rotaxane 11· PF6
e 11· PF6
p
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Anion recognition properties of axle 18· PF6 and rotaxane
19· PF6
w
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T h e a n i o n b i n d i n g p r o p e r t i e s o f a x l e 18· PF6 w e r e
e
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1
0
L. C. Gilday e t a l .
1
Figure 7 (Colour online) H NMR spectra of (a) rotaxane 11·Cl and (b) rotaxane 11·PF6 (300 MHz, CD2Cl2, 298 K).
1
a
f
fi
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(
8
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r
Figure 8 (Colour online) Partial 1H NMR spectra of rotaxane 11·PF6 and various equivalents of TBA·Cl (500 MHz, 1:1 CDCl3:
CD3OD, 293 K).

Supramolecular Chemistry
1 1
T
a
d
b
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l
t
e
i
2
.
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d 18·PF6
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l
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1
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:
1
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18·PF6
m 2
10·PF6c
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2
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1
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Figure 9 (Colour online) Titration curves for the complex for-
mation between rotaxane 11·PF6 and various anions obtained
by monitoring the ortho-pyridinium proton β. 500 MHz, 293
K, 45:45:10 CDCl3:CD3OD:D2O.
b
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d
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Figure 10 (Colour online) Titration curves for the complex
formation between the pyridine axle compound 18·PF6 and
various anions. 1:1 CDCl3:CD3OD, 293 K.
r
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Figure 11 (Colour online) Titration curves for the addition of
various anions to the rotaxane 19·PF6 obtained by following
the axle cavity proton γ. 1:1 CDCl3:CD3OD, 293 K.
a
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1
2
L. C. Gilday e t a l .
Table 3 (Colour online) Association constants and free energy values for the addition of various anions to the rotaxanes 19·PF6 and
20·PF6 in 1:1 CDCl3:CD3OD.
A
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Supramolecular Chemistry
1 3
Figure 12 (Colour online) Titration curves for the addition of various anions to (a) rotaxane 29·PF6, (b) rotaxane 30·PF6 obtained
by following the macrocycle cavity proton b and (c) axle 27·PF6 obtained by monitoring the para-pyridinium proton. 1:1 CDCl3:
CD3OD, 298 K.
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1 7
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m
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¼
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2
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3
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m
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5
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2
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m
L
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r
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l
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4
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I
M
S m/z
8
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þ
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t
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C
l
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H
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s
1
1
5
4
.
6
5
1
)
.
7
8
8
4
5
4

Supramolecular Chemistry
2 1
Pyridinium-3,5-bis-amide hexafluorophosphate axle com-
.
a
vacuo
n
h
y
d
r
o
u
s
M
g
S
O
,
fi
l
t
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r
e
d
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a
n
d
t
h
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s
o
l
v
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n
t
r
e
m
o
v
e
d
i
n
4
pound 28· PF6
.
C
o
m
p
o
u
n
d
2
8
·
I
(
1
6
7
m
g
,
1
4
.
0 mm
w
o
l
)
w
a
s
t
o
g
i
v
e
2
9
·
P
F
a
s
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y
e
l
l
o
w
s
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i
d
i
n y
Hz , a ce to ne -d6) d
q
u
a
n
t
i
t
a
t
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v
e
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l
d
6
1
d
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s
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d
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n
(
C
H
C
l
(
5
0
,
m
L
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n
d
w
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s
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e
d
i
t
h
0
.
1
M
(
4
4
.
5
m
g
,
0
.
0
2 m
(
m
o
l
) .
H
N
M
R
(
n
r
3
0
0
M
-H 4
3
N
H
P
F
1
0
£
2
0
m
L
)
d
r
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e
d
o
d in vacuo
v
e
r
a
n
h
y
d
r
o
u
s
M S
e 28· PF6
g
O ,
4
(
p
p
m
)
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9
.
1
7
1
H
,
b
r
s
,
p
yr
i
d
i
i
u
m
)
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9
.
1
6
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2
H
,
s
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4
6
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a
q
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2
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l
t
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r
e
d
,
a
n
d
t
h
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m
o
v
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o
g
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v
p
y
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n
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m
-H 2&H 6
NH
)
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9
1
s
.
0
3
(
1
H
,
b
s
,
i
s
o
p
h
t
h
a
l
o
y
l
-
H
)
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8
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9
2
4
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s
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o
f
f
-
w
h
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t
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o
l
i
d
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n
8
9
%
y
i
- d6 ) d
e
l
d
(
1
5
.
0
m
g
,
1
1
.
5 m
(
m
o
l
)
.
,
,
,
(
2
H
,
s
,
a
x
l
e
-
)
,
8
.
8
(
2
H
,
d
, J ¼
NH
CH
1
.
6
H
z
,
i
3
7
s
o
p
h
t
h
a
l
o
y
l
-
1
H
N
M
R
(
5
0
0
M
H
z
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D
1
M
S
O
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p
p
m :
N H
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0
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3
1
2
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,
s
s
H 4&H 6
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8
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4
6
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H
3
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r
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m
a
c
r
o
c
y
c
l
e
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8
.
4
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2
H
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s
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x
l
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p
y
r
i
d
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n
i
u
m
- H 2 & H 6
- H 4
)
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0
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1
0
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2
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s
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A
r
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9
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5
9
(
1
H
,
NH
A
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7
.
5
7
(
4
H
,
d
,
J
¼
8
.
5
H
z
,
N
C
)
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7
.
1
4
–
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3
1
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3
0
H
,
m
,
,
,
3
p
y
r
i
d
i
n
i
u
m
)
,
9 5
C H
.
3
(
2
H
,
s
,
–
0
a
m
i
d
e
-
N H
2
C
H
)
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7
.
5
r H
2
(
4
H
,
d
rH)
,
6
.
4
7
(
4
H
,
d
, J ¼
9
.
4
H
z
,
h
y
d
r
o
q
u
i
n
o
n
e-H
(
)
,
6
.
3
7
(
4
H
2
3 J ¼
8
.
4
H
z
,
N
C
)
,
7
.
2
6
7
8
.
3
0
(
1
H
,
m ,
r H
A
)
,
7
.
1
3
–
d
,
3 J ¼
9
.
4
H
z
,
h
y d
-H
r
o
q
u
i
n
o
n
e
-
H
)
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6
. 1
CH3
0
2
H
,
b
r
t
7
.
1
8
(
C H3
6
H
,
m
,
A
r
H
)
,
7
.
0 4
C H2
–
7
.
(
1
2
H
,
m
,
A
)
,
4 4
C H3
.
4
(
3
H
,
3
s
,
3J ¼
2
.
6 H
CH2
z
,
a
l
k
e
n
e
)
,
4
.
5
4
(
3
H
,
CH2
m
,
N
)
,
4
.
0
6
–
4
.
0
7
1
N
N
)
,
4
2
4
.
1
2
8
(
4
H
,
s
,
) ,
- d6
1
.
2
5
(
3
6
H s
- d6 ) d
1
,
,
C
(
)
)
;
C
(
CH2
4
H
,
s
,
,
)
,
3
.
8
4
–
3
.
8
9
(
CH2
8
H
,
m
,
)
,
3
.
7
1
–
3
.
7
4
(
)
4
H
,
m
,
3
M
R
(
1
5
.
M
H
z
,
D
M
S
O
D
M
S
O
(
p
p
m
)
:
1
6
1
.
5
,
,
)
3
.
6
2
–
3 .
CH3
6
4
(
4
H
,
1
m
3
,
)
,
1
.
6
3
(
1
2
H
,
s
,
C
(
C
H
)
,
1
.
2
7
-d6) d
3
2
1
1
4
7
.
9
,
1
7
2
.
3
,
1
4
6
.
8
,
1
4
1
.
6
,
1
3
6
.
5
,
3
2
.
7
,
1
3
0
1
.
9
6
,
1
3
0
.
0
(
3
6
p
H
,
s
,
C
(
)
3
)
;
C
N
M
R
(
7
5
.
5
M
H
z
,
a
c
e
t
o
n
e
2
7
.
6
,
1
4
.
4
,
1
1
8
.
6
,
6
- d6 ) d
3
.
2
,
3
4
: 2
.
0
,
3
1
.
1
;
F
N
M
H
R
(
p
m
)
:
1
7
2
.
6
,
1
6
5
.
8
,
1
6
1
.
3
,
1
5
3
.
8
,
1
5
3
.
6
,
1
5
1
.
5
,
1
1
,
4
3
7
9
.
5
,
,
,
(
4
7
PF6
0
.
6
M
H
z
,
D
M
S
O
(
p
p
m
)
7
0
.
2
(
d
,
J
¼
7
: 2
1
2
z
,
2
4
1
1
7
4
5
.
2
,
,
1
4
3
.
9
,
1
3
7
.
8
,
1
3
7
.
5
,
1
3
5
.
0
,
1
3
3
.
4
,
1
3
2
.
2
,
1
3
1
.
9
,
1
.
6
3
1
)
;
P
N
M
R
(
2
0
2
. 4
, P
M
H
z
,
D
M
S
O
-
d
)
d
(
S m/z
p
p
m
)
1
4
4
.
3
0
.
8
1
2
8
.
7
,
1
2
7
.
0
,
1
2
5
.
8
,
1
2
5
.
6
,
1
2
0
.
1
,
1
1
6
.
2
,
1
1
5
.
9
1
.
7
9
6
1
(
(
s
e t
M 2
p
,
J
¼
7
þ
1
2
H
z
F
)
;
E
S
I
M
:
1
1
5
4
.
6
4
7
0
.
1
,
6
9
.
2
,
6
7
.
3
,
6
4
.
9
,
5
9
.
9
,
5
0
.
5
,
4
- d6 ) d
0
.
9
,
3
5
.
2
,
3
2
.
0
,
2
5
.
3
;
F
6
[
P
F
]
,
C
H
N
O
r
e
q
u
i
r
e
s
1
1
5
4
.
6
5
1
8
)
.
N
M
R
(
2
8
2
.
4
M
PF6
H
z
,
a
c
e
t
o
n e
S m/z
(
p
p
m
)
:
2
7
M 2
1
.
6
(
d
,
,
6
7
8
8
4
5
4
þ
J ¼
7
2
4
.
2
H
z
,
)
;
E
S
I
M
:
1
8
3
1
.
9
4
7
6
(
[
P
F
]
6
C
H
4
N
O
r
e
q
u
i
r
e
s
1
8
3
1
.
9
4
6
6
)
.
1
1
1
2
7
8
1
4
Rotaxane 29· Cl
a
.
C
o
m
p
o
u
n
d 27· Cl
c
(
1
0
0
m
g
,
0
.
0
8
m
m
o
(3b
l
)
)
n
d
v
i
n
y
l
-
a
p
p
e
n
d
e
d
o
m
a
c
r
o
c
y
l
e
p
r
e
c
u
r
s
o
r
c
o
m
p
o
u
n
d
( 6
5
2
.
5
m
g
,
0
.
1
0
m
m
l
)
w
e
r
e
d
i
s
s
o
l
v
e
d
i
n
a
n
h
y
d
r
o
u
s
C
H
C
l
Rotaxane 30· Cl
e
.
C
o
m
p
o
u
n
d 28· Cl
e
(
5
6
.
3
m
g
,
4
7
.
3
m
m
o
l
( 3b
)
,
2
2
(
m
L
)
.
G
r
u
b
b
s
’
I
I
c
a
t
a
l
y
s
t
(
6
.
3
m
g
,
1
0
%
b
y
w
e
i
g
h
t
)
w
a
s
v
i
n
y
l
-
a
p
p
e
n
d
d
6 m
r
m
m
a
c
r
o
c
y
c
l
p
r
e
c
u
r
s
o
r
c
o
m
p
o
u
n
d
)
a
d
d
e
d
a
n
d
t
h
e
r
e
a
c
t
i
o
n
m
i
x
t
u
r
e
s
t
i
r
r
e
d
a
t
r
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o
m
t
e
m
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Supplemental data for this article can be accessed here:
http://dx.doi.org/10.1080/10610278.2015.1075538
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. Chem. Soc. Rev. 2012, 41
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Supramolecular Chemistry
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1–23