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Discrete and polymeric complexes of a macrocyclic pillar ligand in the absence and presence of dicarboxylic acid coligandsElectronic supplementary information (ESI) available: The additional crystal structures, PXRD patterns. CCDC reference numbers 1060987 (H2L), 1060988 (1), 1060989 (2), 1060990 (3), 1060991 (4) and 1060992 (5). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5ce01127b
The macrocyclic pillar ligand, dipyridyldibenzotetraaza[14]annulene (H 2 L ), in the absence and presence of the dicarboxylate coligands, biphenyl-4,4′-dicarboxylic acid (H 2 bpdc) or benzene-1,3-dicarboxylic acid (H 2 bdc), reacts with nickel( ii ), cobalt( ii ) and zinc( ii ) to yield [Ni( L )] (...
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| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
| Online Access: | Get full text |
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| Summary: | The macrocyclic pillar ligand, dipyridyldibenzotetraaza[14]annulene (H
2
L
), in the absence and presence of the dicarboxylate coligands, biphenyl-4,4′-dicarboxylic acid (H
2
bpdc) or benzene-1,3-dicarboxylic acid (H
2
bdc), reacts with nickel(
ii
), cobalt(
ii
) and zinc(
ii
) to yield [Ni(
L
)] (
1
), [Co(
L
)] (
2
), [Co(
L
)]
n
(
3
), {[Zn(H
2
L
)(bdc)]·0.5DMF·1.5H
2
O}
n
(
4
) and {[Co
4
(
L
)
2
(bpdc)
2
]·2DMF·H
2
O}
n
(
5
) displaying both discrete and polymeric structures. Complexes
1
and
2
are isostructural, with the respective low-spin, square-planar metal ions occupying the macrocyclic cavity and bound to the N
4
-donor set of the macrocycle in its doubly deprotonated form. In
3
, the cobalt(
ii
) centre again occupies the macrocyclic cavity, but in this case one axial site is occupied by a pyridyl nitrogen from a second ligand complex, resulting in the formation of an infinite zigzag one-dimensional (1D) structure. Solvothermal reaction between Zn(NO
3
)
2
·4H
2
O, H
2
L
and H
2
bdc afforded the 2D coordination polymer {[Zn(H
2
L
)(bdc)]·0.5DMF·1.5H
2
O}
n
(
4
) in which H
2
L
ligands crosslink 1D (bdc-Zn)
n
wavy backbones
via
Zn-N
pyd
bonds. In contrast, the solvothermal reaction of H
2
L
with Co(NO
3
)
2
·6H
2
O in the presence of H
2
bpdc resulted in formation of the 2-fold interpenetrated 3D coordination polymer, {[Co
4
(
L
)
2
(bpdc)
2
]·2DMF·H
2
O}
n
(
5
), exhibiting a pillared-layer structure. The 3D framework of
5
is based on dicobalt(
ii
) cluster secondary building units (SBUs) to yield a
rob
net in which the bpdc/Co-based 2D nets are cross-linked by Co
L
macrocyclic pillar units; the framework of
5
is thermally stable until 350 °C.
Selected transition metal complexes of the pillar macrocycle dipyridyldibenzotetraaza[14]annulene are reported that include a three-dimensional Co(
ii
) MOF with
rob
topology. |
|---|---|
| ISSN: | 1466-8033 |
| DOI: | 10.1039/c5ce01127b |