Molecular aggregation of novel Zn(II)-salophenpyridyl derivatives

Article abstract of DOI:10.1080/10610278.2013.819976

The synthesis of a series of non-symmetrically substituted zinc(II)-salophenpyridyl [salophenpyridyl = N,N′-2-pyridylenebis- (salicylideneimine)] complexes obtained by reacting RO-substituted salicylaldehydes (R = C₁₀H₂₁ or C₁₆H ₃₃) and 2,3-diaminopyridine is here reported. The molecular aggregation behaviour of these derivatives has been thoroughly studied in the solid state. Five new structures have been isolated and analysed. Interestingly, the crystal structure of the complex 2a@4,4′-bipyridine shows the formation of a porous material, whose structure is formed by neutral open boxes potentially able to host guests of suitable dimensions. 2013

Full text of DOI:10.1080/10610278.2013.819976

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Supramolecular Chemistry
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Molecular aggregation of novel Zn(II)-salophenpyridyl
derivatives
Ilaria Giannicchiab, Gustavo Portalonea & Antonella Dalla Cortab
a Department of Chemistry, Università La Sapienza, Piazzale Aldo Moro 5, 00185 Roma, Italy
b IMC-CNR, Università La Sapienza, Piazzale Aldo Moro 5, 00185 Roma, Italy
Published online: 22 Aug 2013.
To cite this article: Ilaria Giannicchi, Gustavo Portalone & Antonella Dalla Cort (2013) Molecular aggregation of novel Zn(II)-
salophenpyridyl derivatives, Supramolecular Chemistry, 25:9-11, 709-717, DOI: 10.1080/10610278.2013.819976
To link to this article: http://dx.doi.org/10.1080/10610278.2013.819976
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Supramolecular Chemistry, 2013
Vol. 25, Nos. 9–11, 709–717, http://dx.doi.org/10.1080/10610278.2013.819976
Molecular aggregation of novel Zn(II)-salophenpyridyl derivatives
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thoroughly studied in the solid state. Five new structures have been isolated and analysed. Interestingly, the crystal structure
of the complex 2a@4,40-bipyridine shows the formation of a porous material, whose structure is formed by neutral open
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Keywords:
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Introduction
ease of synthesis, ability to form stable complexes with
many metals in a variety of oxidation states, versatility as
receptors (7) and as catalysts for organic transformations
(8). They derive from the condensation of 1,2-
phenylenediamine with two equivalents of salicylalde-
hyde (salicylaldehyde ¼ 2-hydroxybenzaldehyde) even-
tually decorated with different substituents. In their
dianionic form, these ligands possess two covalent and
two coordinative binding sites located in a planar array.
This arrangement allows the equatorial coordination of
transition metals, in which the two apical positions can
be further occupied by ancillary ligands, in an
arrangement similar to that of porphyrins (9). Hence, in
the search of new potentially building blocks for new
materials, the use of metal–salophen frameworks can
take advantage from their versatility and larger
availability (10–12).
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present unique characteristics such as structure regularity,
high porosity, flexibility and in many cases even a
designed pore surface (2). This provides high-perform-
ance pores with unprecedented functionalities for the
resulting material (3, 4) and often the ultimate target is to
reproduce zeolite-like environments around the metal (5).
Moreover, the presence on the metal of available binding
sites capable of interacting with selected guests can in
principle lead to highly selective recognition events and
efficient incorporation of substrates. It is well known, for
example, that a variety of transition metal ions can act as
active centres in catalysed reactions (6). Thus, a
combination of unsaturated metal centres and traditional
porous properties (shape- and size-selectivity) can be
used to create desired, highly useful and tailor-made
properties.
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Results and discussion
s 1 and 2, Chart 1, were prepared following
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a common procedure, Scheme 1. The RO-substituted
salicylaldehydes, R ¼ C10H21 or C16H33, were obtained
through the alkylation of 4-benzyloxyphenol with the
appropriate bromide, subsequent deprotection of the
phenolic hydroxide and formylation. The non-symmetrical
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(salicylideneimine)-1,2-phenylenediamine] ligands have
received considerable attention because of their relative
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q 2 0 1 3 T a y l o r & F r a n c i s

7
1
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I. Giannicchi et al.
N
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1a, R = C10H21
1b, R = C16H33
2a, R = C10H21
2b, R = C16H33
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complexes 1a and 1b were synthesised by combining the
monoimine derivative prepared from 2,3-diaminopyridine
and the RO-substituted salicylaldehyde with 3,5-di-tert-
butylsalicylaldehyde in the presence of Zn(OAc)2.
Compounds 2a and 2b were instead prepared from the
monoimine derivative obtained from 2,3-diaminopyridine,
3,5-di-tert-butylsalicylaldehyde and the corresponding 5-
RO-substituted salicylaldehyde with Zn(OAc)2. Yields of
isolated complexes are quite good and the new derivatives
have been fully characterised.
phenomenon takes place (Figure S1a of the Supplemen-
tary Information, available online). This can be ascribed
to the quite general behaviour in solution of zinc–
salophen complexes to form phenol-bridged dimers (13)
in non-competitive solvents, such as chloroform. The
strong preference of Zn(II) for pentacoordination is
indeed well established and leads in these conditions to
the formation of m2-O-bridging complexes (14). This
happens especially when the substituents in the 3,30
positions of the phenyl side rings are small. Another
possibility that can likely occur in our case is that
aggregation originates from a different interaction mode
that involves the N atom of the original 2,3-diaminopyri-
dine. It has been already reported that an efficient
approach to obtain well-defined nanosized structures can
be the use of the metal–Npyr binding motif to assemble
pyridyl-substituted metallo-porphyrins (15) as well as
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both the H as well as 13C spectra consistent with their
molecular formulations.
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indicating that in this medium an auto-aggregation
O
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1b W = OC16H33, Z = H, Y = tert-Butyl, X = tert-Butyl
2a W = tert-Butyl, Z = tert-Butyl, Y = H, X = OC10H21
2b W = tert-Butyl, Z =tert-Butyl, Y = H, X = OC16H33
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Supramolecular Chemistry
7
1
1
analogous metallo-salophen. The example reported by
Reek and coworkers (16) of a Zn(II)-salpyr [salpyr ¼ N,
N0-3-pyridylenebis-(salicylideneimine)] that assembles
into a molecular vase structure supports this second
hypothesis. As a matter of fact also in our case the N
donor group of the 2,3-diaminopyridine ring can act as a
monodentate ligand and coordinate a second molecule of
zinc complex through axial ligation to the metal. Similar
4
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P 2 1
c
r
i
c
l
i
n
P 2 1
i
c
M
o
n
I2/a
o
c
l
i
n
i
c
T r i g o n a l
R 2 3
S p
a (A)
b (A)
˚
c (A)
a (8)
b (8)
g (8)
e
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[ I . 2s(I)]
r
v
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1
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7
0
.
0
3
2
0
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0
3
8
0
.
0
4
4
R [F 2 . 2s(F 2)] (all data)
WR(F 2) (all data)
0
0
1
4
.
.
.
0
1
0
8
5
6
1
2
7
1
0
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.
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1 . 0 4
4 0 4
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N
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r
a
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s
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8
2
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3
1

7
1
2
I. Giannicchi et al.
( 8 s 1a and 2a.
(2a@DMF/H2O)
˚
S e l e c t e d i n t e r a t om i c d i s t a nc e s ( A) a n d a n g l e s ) f o r c o m p l e x e
T
a
b
l
e
2
.
(
2
a
@
p
y
r
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2
a
@
b
i
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y
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m
o
l
a
)
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1
a
@
D
M
F
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1
a
)
2
2
a
Z
Z
Z
Z
Z
Z
Z
Z
Z
n
n
n
n
n
n
n
n
n
1
1
1
1
1
1
1
1
1
–
–
–
–
–
–
–
–
–
C
C
Z
Z
Z
Z
Z
n
1
1
3
.
0
0
9
0
0
8
4
8
1
1
5(
2(
(
5
2
2
2
)
)
)
)
O
O
O
O
O
N
N
N
7
1
n
n
n
n
1
1
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9
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5
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2
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1
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2
2
1
7 7
57
54
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4
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8
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5
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2
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1
1
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4
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6
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0
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a
–
Z
n
1
–
N
1
5
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a
–
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–
–
–
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–
–
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
Z
n
n
n
n
n
n
n
n
n
n
n
n
n
1
1
1
1
1
1
1
1
1
1
1
1
1
–
–
–
–
–
–
–
–
–
–
–
–
–
O
N
N
N
N
O
O
O
O
O
O
O
O
2
4
4
4
4
4
4
4
4
5
5
5
5
8
(
9 7
01
02
00
. 1
. 1
. 0
. 6
7
(
9
9
9
9
)
)
)
)
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0
9
9
0
2
8
5
0
.
.
.
.
1
8
7
5
4
(
1
1
1
1
2
2
2
2
)
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1
1
9
3
8
(
(
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2(
4(
9(
1
1
1
0
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9
2
6
5
7
.
.
.
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7
3
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8
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0
0
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6
0
4
9
.
.
.
.
1
9
7
3
7
(
1
1
1
1
2
3
3
1
)
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0
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1
1
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9
(
0
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1 0
1 0
1 0
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1
3
5
4
.
.
.
.
0
1
6
1
3
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4
(
8
(
3
(
)
a
T
h
e
s
e
a
t
o
m
s
a
r
e
a
t
s
y
m
m
e
t
r
y
c
o
d
e
:
2
x
þ
2
/
3
,
2
y
þ
1
/
3
,
2
z
þ
4
/
3
.
poorly resolved spectra were obtained also in deuterated
toluene solvent which is unable, as well as chloroform, to
compete with the self-assembly of the Zn(salophen)
complexes. Quite different is instead the spectrum in d6-
acetone characterised by a very good resolution indicating
that acetone can effectively compete with the dimerisation
process (Figure S1b of the Supplementary Information,
available online). The addition of a small amount of
pyridine to the chloroform solution of the complexes
leads to a well-resolved spectra because pyridine acts as a
Lewis base favouring the formation of the monomer
through axial ligation of the N-donor ligand (17).
studies are reported in Tables 1 and 2 and visualised in
Figures 1–6.
F
i
r
s
t
o
f
f
a l l , c r y s t a l li s a t io n f r o m a c e t o n e l e a d s t o t he
a d i m e r w h o s e m o l e c u l a r s t r u c t u r e i s g iv e n i n
i
s
o
l
a
t
i
o
n
o
F
i
g
u
r
e
1
.
T
h
e
o
b
t
a
i
n
e
d
m
o
l
e
c
u
l
a
r
s
t
r
u
c
t
u
r
e
o
f
(
1
a
)
r
e
p
r
e
s
e
n
t
s
a
n
2
interesting finding because it is generally assumed that
bulky tert-butyl groups at the ortho position to the phenolic
oxygens of the salophen ligand prevent self-association of
this type. This homodimer is based on the axial
coordination of two symmetry-equivalent phenolic oxygen
atoms, O2 and O20, (see Scheme 2 for numbering) of the
two zinc–salophen monomers through the formation of a
m2-O-bridging bond between the two salophen ligands and
the two zinc centres. Cofacial homodimers, in which the
two zinc centres are involved in a four-point interaction
and one of the phenolic oxygen atoms of each molecule
bridges in an axial-ligand fashion to its dimeric partner
molecule, are believed to give a highly stable assembled
state (18). The axial oxygen coordination gives rise to a
distorted square pyramidal Zn-coordination. The dimer
A
s
i
t
i
s
q
u
i
t
e
d
i
f
fi
c
u
l
t
t
o
h
d
i
s
t
i
n
g
u
i
s
h
b
e
t
w
e
e
n
t
h
e
t
w
o
n
o
p
o
s
s
i
b
l
e
b
i
n
d
i
n
g
m
o
t
i
f
s
t
a
t
l
e
a
d
t
o
a
u
t
o
a
s
s
e
m
b
l
y
i
s
o
l
u
t
i
o
n
,
s
o
l
i
d
-
s
t
a
t
e
s
t
u
d
i
e
o v i d e h i n t s o n t h i s i s s u e .
s
c
a
n
b
e
e
x
t
r
e
m
e
l
y
u
s
e
f
u
l
t
p
r
U
n
f
o
r
t
u
n
a
t
e
l
y
,
i
t
w
a
s
n
o
t
p
o
s
c o m p o u n d s 1b and 2b, i.e. those with the C16H33
s
i
b
l
e
t
o
o
b
t
a
i
n
c
r
y
s
t
a
l
s
o
f
chains, suitable for X-ray analysis. Single crystals of 1a
and 2a were instead successfully obtained and analysed
by X-ray diffraction. The results of the crystallographic

Supramolecular Chemistry
7
1
3
F
i
g
u
r
e
1
.
X
-
r
a
y
m
o
l
e
c
u
l
a
r
s
t
drawn at 50% probability level. H atoms have been omitted for clarity.
r
u
c
t
u
r
e
f
o
r
c
o
m
p
l
e
x
(
1
a
)
,
p
a
r
t
i
a
l
l
y
s
h
o
w
i
n
g
t
h
e
a
t
o
m
-
l
a
b
e
l
l
i
n
g
s
c
h
e
m
e
.
D
i
s
p
l
a
c
e
m
e
n
t
s
e
l
l
i
p
s
o
i
d
s
a
r
e
2
F
i
g
u
r
e
2
.
X
-
r
a
y
m
o
l
e
c
u
l
a
50% probability level. H atoms have been omitted for clarity. The rotational disorder in one of the two tert-butyl groups is not shown.
r
s
t
r
u
c
t
u
r
e
f
o
r
(
2
a
@
p
y
r
)
,
p
a
r
t
i
a
l
l
y
s
h
o
w
i
n
g
t
h
e
a
t
o
m
-
l
a
b
e
l
l
i
n
g
s
c
h
e
m
e
.
D
i
s
p
l
a
c
e
m
e
n
t
s
e
l
l
i
p
s
o
i
d
s
a
r
e
d
r
a
w
n
a
t
F
i
g
u
r
e
3
50% probability level. H atoms have been omitted for clarity.
.
X
-
r
a
y
m
o
l
e
c
u
l
a
r
s
t
r
u
c
t
u
r
e
f
o
r
(
1
a
@
D
M
F
)
,
p
a
r
t
i
a
l
l
y
s
h
o
w
i
n
g
t
h
e
a
t
o
m
-
l
a
b
e
l
l
i
n
g
s
c
h
e
m
e
.
D
i
s
p
l
a
c
e
m
e
n
t
s
e
l
l
i
p
s
o
i
d
s
a
r
e
d
r
a
w
n
a
t
formation originates a non-symmetrical positioning of the
Zn ion in the N2O2 coordination pocket. Consequently, in
the dimeric structure there are three distinct Zn–O
distances: Zn1–O1, which is equal to 1.945(2), whereas
atom (14b). The two salophen units have a nearly anti-
parallel orientation and the tert-butyl groups of the
individual molecules point away from the adjacent unit in
order to minimise steric repulsion.
0
˚
Zn1–O2 and Zn1–O2 amount to 2.082(2) and 2.013(2) A,
R e d s i n g l e c r y s t a l s o f 1a and 2a suitable for X-ray
diffraction were obtained by slow growth from pyridine
(Figure 2), N,N0-dimethylformamide (DMF) (Figure 3),
respectively. As expected, the shortest of these distances is
the one between the zinc atom and the unbridged oxygen

7
1
4
I. Giannicchi et al.
F
i
g
u
r
e
4
.
T
h
e
a
s
y
m
m
e
50% probability level. Non-water H atoms have been omitted for clarity. Intermolecular hydrogen bond is indicated by double-dashed lines.
t
r
i
c
u
n
i
t
f
o
r
2
a
@
D
M
F
/
H
O
,
p
a
r
t
i
a
l
l
y
s
h
o
w
i
n
g
t
h
e
a
t
o
m
-
l
a
b
e
l
l
i
n
g
s
c
h
e
m
e
.
D
i
s
p
l
a
c
e
m
e
n
t
s
e
l
l
i
p
s
o
i
d
s
a
r
e
d
r
a
w
n
a
t
2
F
i
g
u
r
e
5
.
X
-
r
a
y
m
o
l
e
c
u
l
a
r
s
t
r
ellipsoids are drawn at 50% probability level. H atoms have been omitted for clarity.
u
c
t
u
r
e
f
o
r
s
a
l
o
p
h
e
n
(
2
a
)
@
b
i
p
y
r
i
d
i
n
e
,
p
a
r
t
i
a
l
l
y
s
h
o
w
i
n
g
t
h
e
a
t
o
m
-
l
a
b
e
l
l
i
n
g
s
c
h
e
m
e
.
D
i
s
p
l
a
c
e
m
e
n
t
s
2
F
i
g
u
r
e
6
.
P
a
r
t
o
f
t
h
e
c
r
y
s
t
a
l
s
t
r
u
c
t
u
r
e
o
f
2
a
@
b
i
p
y
r
i
d
i
n
e
i
n
t
h
e
s
o
l
i
d
s
t
a
t
e
.
C
a
t
o
m
s
a
r
e
s
h
o
w
n
a
s
s
m
a
l
l
s
p
h
e
r
e
s
o
f
a
r
b
i
t
r
a
r
y
s
i
z
e
.
2
2

Supramolecular Chemistry
7
1
5
DMF/water (Figure 4), 4,40-bipyridine (Figures 5 and 6),
as several attempts to obtain them in less polar and
donating solvents failed.
o
b
t
a
i
n
e
d
d
e
r
i
v
a
t
i
v
e
s
a
u
t
o
a
s
s
e
m
b
l
e
i
n
n
o
n
-
c
o
m
p
e
t
i
t
i
v
e
e
e
c
a
o
o
r
d
i
n
a
t
i
n
g
s
o
l
v
e
n
t
s
.
T
o
v
e
r
i
f
y
t
h
e
h
y
p
o
t
h
e
s
i
s
t
h
a
t
t
h
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t
o
a
s
s
e
m
b
l
y
c
o
u
l
d
b
e
t
h
e
r
e
s
u
l
t
o
f
t
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e
c
o
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r
d
i
n
a
t
i
o
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e
o
f
t
I
n
a
l
l
t
h
e
c
a
r
y
s
t
a
l
s
,
t
h
e
m
o
l
e
c
u
l
a
r
s
t
r
u
c
t
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s
t
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e
n
i
t
r
o
g
e
n
a
t
o
m
o
f
t
h
e
2
,
3
-
d
i
a
m
i
n
o
p
y
r
i
d
i
l
r
a
t
i
n
g
o
f
o
n
z
i
n
c
–
z
i
n
c
a
t
o
m
i
n
fi
v
e
-
c
o
n
o
r
d
i
n
a
t
e
d
i
s
t
o
r
t
e
d
s
q
u
a
r
e
p
y
r
a
m
i
d
a
l
s
a
l
o
p
h
e
n
c
o
m
p
l
e
x
w
i
t
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t
h
e
m
e
t
a
l
c
e
n
t
r
e
o
f
s
e
c
o
n
d
m
o
l
e
c
u
l
e
e
-
g
e
o
m
e
t
r
y
.
T
h
e
p
r
e
s
e
c
e
o
f
s
t
r
o
n
g
d
o
n
a
t
i
n
g
a
d
d
i
t
i
v
e
s
i
n
o
f
z
i
n
c
c
o
m
p
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e
x
t
h
r
o
u
g
h
a
x
i
a
l
l
i
g
a
t
i
o
n
o
t
h
e
m
e
t
a
l
,
w
s
o
l
u
t
i
o
n
p
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v
e
n
t
e
d
a
n
y
p
o
s
s
i
b
i
l
i
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y
t
o
o
b
t
a
i
n
c
o
m
p
l
e
x
e
s
o
t
h
e
r
c
a
r
r
i
e
d
o
z
u
t
s
o
l
i
d
-
s
t
a
t
e
s
t
u
d
i
e
s
.
F
i
v
e
n
e
w
s
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r
u
c
t
u
r
e
s
c
o
m
p
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s
t
t
h
a
n
t
h
o
s
e
i
n
w
h
i
c
h
t
h
e
p
o
t
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n
t
i
a
l
g
u
e
s
t
s
w
e
r
e
c
o
o
r
d
i
n
a
t
e
d
t
o
i
n
g
t
h
e
i
n
c
–
s
a
l
o
p
h
e
n
c
o
m
p
o
u
n
d
s
1
a
a
n
d
2
a
w
e
r
e
i
s
o
l
a
t
e
d
h
e
m
e
t
a
l
.
I
n
t
h
e
m
o
n
o
m
e
r
i
c
c
o
m
p
l
e
x
e
s
,
p
y
r
i
d
i
n
e
,
4
,
40
-
and analysed. Unfortunately, none of them gave an answer to
our question, but unexpectedly provided a quite interesting
finding. Crystallisation of compound 2a in the presence of
4,40-bipyridine leads to the formation of a neutral open-
box structure whose dimensions are fixed by the Zn–Zn
˚
distance within building blocks on the one hand (8.2A) and
by the distance between the nitrogen donors of the ditopic
b
p
i
p
y
r
i
d
i
n
e
,
D
M
F
c
a
n
d
H
O
,
r
e
s
p
e
c
t
i
v
e
l
y
,
o
c
c
u
p
y
t
h
e
a
p
i
c
a
l
2
o
s
i
t
i
o
n
o
f
t
h
e
o
m
p
l
e
x
(
F
i
g
u
r
e
s
2
–
5
)
.
T
h
i
s
i
s
s
i
m
i
l
a
r
t
o
w
h
a
t
w
a
s
o
b
s
e
r
v
e
d
f
o
r
a
n
a
l
o
g
o
u
s
Z
n
–
s
a
l
o
p
h
e
n
c
o
m
p
l
e
x
e
s
(18), where oxygen and nitrogen donor ligands such as
DMF, H2O and pyridine have been reported to coordinate at
the axial position. The Zn atoms are 0.358(1), 0.332(1),
˚
0.378(1) and 0.311(1) and 0.355(2) A, respectively, above
the plane formed by the N2O2 coordination.
˚
ligand (11.3 A) on the other hand. The porous material
obtained in this way is basically formed by boxes with a
˚
diameter of 13.9A, potentially able to host–guests of
I
n
t
h
e
c
o
m
p
Zn–O (solvent) distances (2.067(2), 2.062(2) and 2.102
l
e
x
e
s
2
a
@
D
M
F
/
H
O
a
n
d
1
a
@
D
M
F
,
t
h
e
2
suitable dimensions. The wide variety of applications
generally associated with this kind of metal-organic
framework makes this result quite promising by showing
the potentialities of combining metal salophen-type com-
plexes with porosity.
˚
(3) A, respectively, are significantly longer than the Zn–O
(ligand) distances (1.937(2), 1.964(2), 1.957(2), 1.958(2),
˚
1.982 (2) and 1.938(3) A). The same trend is not observed
for the bonds to nitrogen in compounds 2a@pyridine and
(2a)2@4,40-bipyridine.
A
l
t
h
o
u
g
h
i
n
t
e
r
e
s
t
i
n
g
a
n
d
i
n
f
o
r
m
a
t
i
v
e
,
t
h
e
i
s
o
l
a
t
i
o
n
o
f
Experimental
s
u
c
h
c
o
m
p
l
e
x
e
s
d
i
d
n
o
t
r
e
v
e
a
l
t
h
e
p
o
s
s
i
b
l
e
i
n
v
o
l
v
e
m
e
n
t
i
n
t
h
e
c
o
o
r
d
i
n
a
t
i
o
n
e
o
f
t
h
.
e
n
i
t
r
o
g
e
n
d
o
n
o
r
g
r
o
u
p
o
f
t
h
e
2
,
3
-
G
e
n
e
r
a
l
p
r
o
c
e
d
u
r
e
f
o
r
m
o
n
o
i
m
i
n
e
s
y
n
t
h
e
s
i
s
- n-alkyloxybenzaldehyde
:
2
,
3
-
d
i
a
m
i
n
o
-
d
o
i
a
m
i
n
o
p
y
r
i
d
i
n
r
i
n
g
p
y
r
i
d
i
n
e
(
3
m
m
o
l
)
,
2
-
h
y
d
r
o
x
y
,
5
I
n
s
t
e
a
d
,
u
n
e
x
p
e
c
t
e
d
l
y
,
t
h
e
c
r
y
s
t
a
l
s
t
r
u
c
t
u
r
e
o
f
t
h
e
c
o
m
p
l
e
x
(1 mmol) in methanol (10 ml) were stirred at room
temperature for 24 h. The mixture was filtered and the
isolated solid was purified by flash column chromatog-
raphy (silica gel, chloroform:ethylacetate, 7:3).
0
f
2
a
o
b
t
a
i
n
e
d
i
n
t
h
e
p
r
e
s
e
n
c
e
o
f
4
,
4
-
b
i
p
y
r
i
d
i
n
e
s
h
o
w
e
d
t
h
e
most interesting structure of the lot, Figures 5 and 6.
o
I
t
i
s
f
o
r
m
e
d
b
y
t
w
o
z
i
n
c
–
s
a
l
p
h
e
n
b
u
i
l
d
i
n
g
b
d
d
l
o
c
k
s
c
o
n
n
e
c
t
e
d
b
y
t
h
e
b
e
i
p
y
r
i
d
y
l
d
i
t
o
p
i
c
l
i
g
a
n
d
w
h
e
r
e
,
u
e
t o
n
M
o
n
o
i
m
i
n
e
o
f
5
-
(
d
e
c
y
l
o
x
y
)
s
a
l
i
c
y
l
a
l
d
e
h
y
d
e
,
3
a
.
Y
i
e
l
d
s
t
e
r
i
c
r
e
p
u
l
s
i
o
n
,
t
h
t
w
o
h
C
a l
0
k
y
l
c
h
a
i
n
s
a
r
e
o
r
i
e
n
t
e
i
n
t
a
82% (0.99 g). 1H NMR (300 MHz in CD3COCD3), d 11.99
(s, 1H, OH), 8.77 (s, 1H, CH), 7.89 (dd, J1 ¼ 4.9 Hz,
J2 ¼ 1.5 Hz, 1H, CH), 7.38 (dd, J1 ¼ 7.5 Hz, J2 ¼ 1.5 Hz,
1H, CH), 7.13 (d, J ¼ 3.3 Hz, 1H, CH), 7.00 (dd,
J1 ¼ 9 Hz, J2 ¼ 3.3 Hz, 1H, CH), 6.84 (d, J ¼ 9 Hz, 1H,
CH), 6.64 (dd, J1 ¼ 7.5 Hz, J2 ¼ 4.9 Hz, 1H, CH), 5.45
(bs, 2H, NH2), 3.94 (t, J ¼ 6.3 Hz, 2H, CH2), 1.42–1.26
(m, 16H, CH2), 0.83 (t, J ¼ 6.3 Hz, 3H, CH3). 13C NMR
(300 MHz in CD3COCD3), d 163.81, 154.71, 152.61,
151.81, 146.28, 144.50, 130.90, 125.28, 121.81, 118.43,
117.83, 116.04, 113.94, 68.69, 31.62, 29.31, 29.29, 29.12,
29.04, 25.76, 22.41, 13.85. Anal. calcd for C22H31O2N3:
11.37 N%; 71.51 C%; 8.46 H%. Found: 11.34 N%; 71.16
C%; 8.29 H%.
1
a
a
n
t
i
p
a
r
a
l
l
e
l
f
a
s
h
i
o
n
.
T
e
p
a
c
k
i
n
g
d
i
a
g
r
a
m
s
h
o
w
x
-
s
f
o
r
h
i
s
s
s
e
i
m
b
l
y
t
h
e
f
o
r
t
m
a
t
i
o
n
o
f
a
n
e
u
t
r
a
l
o
p
e
n
-
b
o
s
t
r
u
c
t
i
u
r
e
w
h
c
h
c
o
n
fi
r
m
s
h
e
p
o
t
i
e
n
t
i
a
l
i
t
y
o
f
fl
e
x
i
b
l
e
4
,
4 0
b
i
p
y
r
d
y
l
l
i
g
a
n
d
s
t
o
y
i
e
l
d
c
y
c
l
i
c
d
m
e
r
s
b
y
2
þ
2 c o o r d i n a t i o n , l ik e i n
d
t
h
i
s
c
a
s
e
,
o
r
3
þ
3
s
e
l
f
-
a
s
s
e
m
b
l
y
i
n
a
c
c
o
r
a
n
c
e t
( 19). The
w
i
h
t
h
e
c
o
o
r
d
i
n
a
t
i
o
n
g
e
o
m
e
t
r
y
o
f
t
h
e
i
n
v
dimensions of this box are fixed by the Zn–Zn distance
o
l
v
e
d
m
e
t
a
l
˚
within building blocks on the one hand (8.2 A) and on the
other hand by the distance between the nitrogen donors of
the ditopic ligand, which controls the distance between the
˚
two Zn–salophen units (11.3 A). So this results in a box
˚
diameter of 13.9 A. As a consequence, the packing of the
molecular boxes leads to a porous material with channels in
one direction along the crystallographic b-axis, Figure 6.
M
o
n
o
i
m
i
n
e
o
f
5
-
(
h
e
x
a
d
e
c
y
l
o
x
y
)
s
a
l
i
c
y
l
a
l
d
e
h
y
d
e
,
3
b
.
Yield 46% (0.58 g). 1H NMR (300MHz in CD3COCD3), d
11.99 (s, 1H, OH), 8.77 (s, 1H, CH), 7.89 (dd, J1 ¼ 4.9 Hz,
J2 ¼ 1.5 Hz, 1H, CH), 7.38 (dd, J1 ¼ 7.5 Hz, J2 ¼ 1.5 Hz,
1H, CH), 7.13 (d, J ¼ 3.3 Hz, 1H, CH), 7.01 (dd, J1 ¼ 9 Hz,
J2 ¼ 3.3 Hz, 1H, CH), 6.84 (d, J ¼ 9 Hz, 1H, CH), 6.64 (dd,
J1 ¼ 7.5 Hz, J2 ¼ 4.9 Hz, 1H, CH), 5.45 (bs, 2H, NH2), 3.95
(t, J ¼ 6.3 Hz, 2H, CH2), 1.45–1.24 (m, 26H, CH2), 0.83 (t,
Conclusions
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7
1
6
I. Giannicchi et al.
J ¼ 6.3 Hz, 3H, CH3). 13C NMR (300MHz in CD3COCD3),
d 166.45, 155.06, 152.11, 151.09, 134.81, 127.98, 123.52,
118.27, 117.87, 116.28, 112.89, 68.75, 31.63, 29.40, 29.31,
29.10, 29.06, 28.99, 25.74, 22.39, 13.82. Anal. calcd for
C28H43O2N3: 9.26 N%; 74.13 C%; 9.55 H%. Found: 8.98 N
%; 73.73 C%; 9.28 H%.
134.43, 133.94, 129.57, 124.81, 124.30, 123.42, 121.59,
118.37, 117.87, 116.59, 68.19, 34.96, 33.20, 31.43, 30.48,
25.65, 22.13, 13.17. MS (ESI-TOF): m/z calc. [M þ H]þ
732.4083; m/z found [M þ H]þ 732.4082.
1
x 2a. Yield 64% (0.32 g). H NMR (300 MHz
C
o
m
p
l
e
in CD3COCD3), d 9.42 (s, 1H, CH), 9.00 (s, 1H, CH), 8.31
(dd, J1 ¼ 4.9 Hz, J2 ¼ 1.5 Hz, 1H, CH), 8.22 (dd,
J1 ¼ 8.1 Hz, J2 ¼ 1.5 Hz, 1H, CH), 7.38–7.31 (m, 2H,
CH), 7.13 (d, J ¼ 2.7 Hz, 1H, CH), 6.94 (dd, J1 ¼ 9 Hz,
J2 ¼ 3.3 Hz, 1H, CH), 6.88 (d, J ¼ 3.3 Hz, 1H, CH), 6.68
(d, J ¼ 9 Hz, 1H, CH), 3.93 (t, J ¼ 6.6 Hz, 2H, CH2),
1.75–1.70 (m, 2H, CH2), 1.41 (s, 9H, CH3), 1.40–1.25 (m,
23H, CH2 and CH3), 0.83 (t, J ¼ 6.3 Hz, 3H, CH3). 13C
NMR (300 MHz in CD3COCD3), d 171.29, 163.92,
162.73, 150.05, 147.75, 145.09, 141.32, 135.10, 133.74,
129.02, 128.99, 126.04, 124.76, 123.19, 122.15, 118.21,
117.70, 116.36, 68.10, 34.99, 33.20, 31.45, 30.53, 29.43,
29.03, 28.96, 27.89, 25.69, 22.14, 13.17. Anal. calcd for
C37H49O3N3Zn: 6.47 N%; 68.45 C%; 7.61 H%. Found:
6.36 N%; 67.72 C%; 7.67 H%. MS (ESI-TOF): m/z calc.
[M þ H]þ 647.3092; m/z found [M þ H]þ 647.3073.
M
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1
Yield 26% (0.56 g). H NMR (300 MHz in CD3COCD3),
d 13.24 (s, 1H, OH), 8.83 (s, 1H, CH), 7.90 (dd,
J1 ¼ 4.9 Hz, J2 ¼ 1.5 Hz, 1H, CH), 7.49–7.41 (m, 3H,
CH), 6.66 (dd, J1 ¼ 7.5 Hz, J2 ¼ 4.9 Hz, 1H, CH), 5.45
(bs, 2H, NH2), 1.43 (s, 9H, CH3), 1.30 (s, 9H, CH3). 13C
NMR (300 MHz in CD3COCD3), d 165.11, 157.42,
152.09, 142.49, 140.63, 136.63, 131.06, 128.51, 126.52,
125.22, 117.57, 113.41, 34.48, 33.58, 30.75, 28.73. Anal.
calcd for C20H27ON3: 12.91 N%; 73.81 C%; 8.36 H%.
Found: 12.64 N%; 73.56 C%; 7.92 H%.
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.
CD3COCD3), d 9.43 (s, 1H, CH), 9.01 (s, 1H, CH), 8.30 (dd,
J1 ¼ 4.9 Hz, J2 ¼ 1.5 Hz, 1H, CH), 8.23 (dd, J1 ¼ 8.1 Hz,
J2 ¼ 1.5 Hz, 1H, CH), 7.38–7.32 (m, 2H, CH), 7.14 (d,
J ¼ 2.7 Hz, 1H, CH), 6.96 (dd, J1 ¼ 9 Hz, J2 ¼ 3.3 Hz, 2H,
CH), 6.88 (d, J ¼ 3.3 Hz, 1H, CH), 6.68 (d, J ¼ 9 Hz, 1H,
CH), 3.93(t, J ¼ 6.6 Hz, 2H, CH2), 1.75–1.70(m, 2H, CH2),
1.41 (s, 9H, CH3), 1.37–1.26 (m, 35H, CH2 and CH3), 0.84
(t, J ¼ 6.3 Hz, 3H, CH3). 13C NMR (300MHz in CD3-
COCD3), d 163.80, 162.52, 147.45, 145.03, 141.38, 135.08,
133.67, 129.03, 128.98, 126.27, 124.80, 123.18, 118.91,
117.35, 116.35, 68.16, 34.99, 33.20, 30.53, 25.67, 22.12,
13.16. MS (ESI-TOF): m/z calc. [M þ H]þ 732.4083; m/z
found [M þ H]þ 732.4056.
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d (20).
x 1a: Yield 70% (0.27 g). H NMR (300 MHz
e
s
1
C
o
m
p
l
e
in CD3COCD3), d 9.40 (s, 1H, CH), 8.97 (s, 1H, CH), 8.35
(dd, J1 ¼ 4.9 Hz, J2 ¼ 1.5 Hz, 1H, CH), 8.16 (dd,
J1 ¼ 8.1 Hz, J2 ¼ 1.5 Hz, 1H, CH), 7.37–7.31 (m, 2H,
CH), 7.11 (d, J ¼ 2.7 Hz, 1H, CH), 6.90–6.82 (m, 2H,
CH), 6.61 (d, J ¼ 9 Hz, 1H, CH), 3.85 (t, J ¼ 6.3 Hz, 2H,
CH2), 1.72–1.65 (m, 2H, CH2), 1.41 (s, 9H, CH3), 1.40–
1.27 (m, 23H, CH2 and CH3), 0.84 (t, J ¼ 6.3 Hz, 3H,
CH3). 13C NMR (300 MHz in CD3COCD3), d 172.29,
163.27, 150.69, 148.04, 145.95, 141.37, 134.45, 133.99,
129.61, 129.58, 124.74, 124.35, 123.49, 121.64, 118.5,
117.88, 116.57, 68.14, 34.95, 33.20, 31.45, 30.46, 25.66,
22.14. Anal. calcd for C37H49O3N3Zn: 6.47 N%; 68.45 C
%; 7.61 H%. Found: 6.23 N%; 67.77 C%; 7.26 H%. MS
(ESI-TOF): m/z calc. [M þ H]þ 647.3092; m/z found
X-ray structure determinations
R
e
d
s
i
n
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l
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t
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were obtained by slow growth from pyridine, bipyridine
and DMF/water, whereas crystals of 1a were obtained
from acetone and DMF. The intensity data were collected
on the Oxford Diffraction Xcalibur S CCD diffracto-
meter with graphite-monochromated Mo Ka radiation
[M þ H]2 647.3088.
˚
(l ¼ 0.71069 A) at 298(2) K operated at 50 kV and
1
x 1b. Yield 77% (0.44 g). H NMR (300 MHz
C
o
m
p
l
e
40 mA. The data reduction was carried out using the
CrysAlis software package (21). Solution, refinement and
analysis of the structures were done using the programs
integrated in the WinGX system (22). The structures were
solved by direct methods (SIR2002) (23) and refined by
the full-matrix least-squares method based on F 2
(SHELXL-97) (24). In (2a@pyr), the tert-butyl group at
C35 was rotationally disordered. The non-hydrogen
atoms were refined anisotropically till convergence was
reached. All the hydrogen atoms were located in a
in CD3COCD3), d 9.38 (s, 1H, CH), 8.96 (s, 1H, CH), 8.35
(dd, J1 ¼ 4.9 Hz, J2 ¼ 1.5 Hz, 1H, CH), 8.15 (dd,
J1 ¼ 8.1 Hz, J2 ¼ 1.5 Hz, 1H, CH), 7.36–7.32 (m, 2H,
CH), 7.09 (d, J ¼ 2.7 Hz, 1H, CH), 6.89–6.82 (m, 2H,
CH), 6.58 (d, J ¼ 9 Hz, 1H, CH), 3.84 (t, J ¼ 6.6 Hz, 2H,
CH2), 1.73–1.70 (m, 2H, CH2), 1.41 (s, 9H, CH3),
1.37–1.25 (m, 35H, CH2 and CH3), 0.83 (t, J ¼ 6.3 Hz,
3H, CH3). 13C NMR (300 MHz in CD3COCD3), d 172.35,
167.39, 163.63, 163.1, 150.67, 147.86, 145.85, 141.45,

Supramolecular Chemistry
7
1
7
(
5
)
B
R
r a d s h a w , D . ; C l a r i d g e , J . B . ; C u s s e n , E . J . ; P r i o r , T . J . ;
o s s e i n sk y , M . J . Acc. Chem. Res., 2005, 38, 273–282;
difference Fourier map. In the complex 2a@DMF/H2O,
those belonging to water molecules were refined
isotropically. The remaining hydrogen atoms were
introduced in the final refinement with idealised geometry
and allowed to ride on the C/N atoms to which they were
attached; their thermal parameters were tied to those of
the parent C/N atoms. Geometrical calculations were
carried out using PLATON (25). The figures were
prepared using ORTEP-3 (26).
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Supporting Information Available
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o
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f
´
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