Inclusion of metal-organic complexes into cucurbit[8]uril Novosibirsk 2005 Tatiana V. Mitkina Nikolaev Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberian Branch, Acad. Lavrentiev Av. 3, 630090, Novosibirsk/Russia; [email protected]
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Inclusion of metal-organic complexes into cucurbit[8]uril
Nikolaev Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberian Branch, Acad. Lavrentiev Av. 3, 630090, Novosibirsk/Russia; [email protected]. Inclusion of metal-organic complexes into cucurbit[8]uril. Tatiana V. Mitkina. - PowerPoint PPT Presentation
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Inclusion of metal-organic complexes into cucurbit[8]uril
Inclusion of metal-organic complexes into cucurbit[8]uril
Novosibirsk2005
Tatiana V. Mitkina
Nikolaev Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberian Branch,
Acad. Lavrentiev Av. 3, 630090, Novosibirsk/Russia; [email protected]
cucurbit[8]uril (CB[8])C48H48N32O16
cucurbit[n]urilС6nH6nN4nO2n
n = 5 10symmetry Dnh
The family of cucurbit[n]urils (CB[n])The family of cucurbit[n]urils (CB[n])
17.5 Å
8.8 Å
6.9 Å
9.1 Å
dimensions of CB[8] molecule
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M
LL
NHNH2H2N
L
NH
NH NH
HN
M
NH2
NH2
M
H2N
H2N
L
L
Guests:
Possible approaches to synthesis of inclusion compounds of metal-organic
complexes into CB[8]
Possible approaches to synthesis of inclusion compounds of metal-organic
complexes into CB[8]
1) “metal aqua-complex + ligand@CB[8]” scheme
2) direct reaction “host + guest”
3) “guest substitution” approach
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+ Ni2+
12-fold excess of NiCl2·6H2O
yellow crystals, yield = 89%,
hot water soluble
Synthesis of {[Ni(cyclam)]@CB[8]}Cl2 ·16H2OSynthesis of {[Ni(cyclam)]@CB[8]}Cl2 ·16H2O
NHNH
NH NH
NN
NN
Ni
cyclam@CB[8]· 4HCl18H2O
1) The approach “metal aqua-complex + ligand@CB[8]”
Aqueous solution, reflux,
100°C, 2 h.
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The structure of {[Ni(cyclam)]@CB[8]}Cl2·16H2OThe structure of {[Ni(cyclam)]@CB[8]}Cl2·16H2O55
X-ray: square-planar environment of NiII; the angle between NiN4 plane and equatorial plane of CB[8] ~ 70°
ESI-MS: m/z = 793.245 {[Ni(cyclam)] + CB[8]}2+
Absorption spectra comparison:
side view
IR: CB[8] vibrations
NiII/NiIII oxidation within the CB[8] cavity. Synthesis of {[NiIII(cyclam)]@CB[8]}(SO4)1.5·14⅔H2O
NiII/NiIII oxidation within the CB[8] cavity. Synthesis of {[NiIII(cyclam)]@CB[8]}(SO4)1.5·14⅔H2O