Double stranded helicates metal binding domain bridge - - PowerPoint PPT Presentation

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Double stranded helicates metal binding domain bridge - - PowerPoint PPT Presentation

Oct 18, 2022 185 likes •985 views

Double stranded helicates metal binding domain bridge substitution pattern Double helicates Triple stranded helicates - Ni(II) : octahedral geometry - one ligand can not wrap around one Ni(II) cation : trimerization - other metals: Co(II),

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binding domain bridge metal

Double stranded helicates

substitution pattern

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Double helicates

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  • Ni(II) : octahedral geometry
  • one ligand can not wrap around one Ni(II) cation : trimerization
  • other metals: Co(II), Fe(II), lanthanides

Triple stranded helicates

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Double and Triple Helicates: an example of Selective-Recognition

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Cyclic Helicates

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1H-NMR

ESI-MS

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2X2 Cu(I) grid

Molecular Grids

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Molecular Grids

3X3 Ag(I) grid

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[n]Catenanes [n]rotaxanes

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knots

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[n]Catenani

Sauvage 1983 Williamson ether synthesis Yield 42%

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Reaction year A B h/c catalyst Glaser 1869 RC≡CH sp RC≡CH sp homo Cu Ullmann 1901 Ar-X sp² Ar-X sp² homo Cu Sonogashira 1975 RC≡CH sp R-X sp³ sp² cross Pd and Cu Negishi 1977 R-Zn-X sp³, sp², sp R-X sp³ sp² cross Pd or Ni Stille 1978 R-SnR3 sp³, sp², sp R-X sp³ sp² cross Pd Suzuki 1979 R-B(OR)2 sp² R-X sp³ sp² cross Pd Hiyama 1988 R-SiR3 sp² R-X sp³ sp² cross Pd Buchwald- Hartwig 1994 R2N-R SnR3 sp R-X sp² cross Pd

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[2]Rotaxani

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catione paraquat Bis-parafenilene-[34]-crown-10

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acilazione 20%

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Hydrophobic effect

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Hydrophobic effect

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Anion templating

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Anion templating

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Halogen bond templating

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Catenani

1mM 50mM

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three identical rings. Each ring is inside a second one and outside the third one. No catenation. 4 connections: endo/eso/endo/eso

Borromean Rings

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Nodo Borromeo

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N O O

: endo-tridentate (2,6 diformilpyiridine DFP)

N N O O H2N NH2

: exo-bidentate

(diamminobipyridiyl ligand DAB)

N N O O N N N N O O N N N N

5-coordinated Zn(II) (sale triflouroacetatato) reversibile imine bond 4+4 macrocyclizatione reaction

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endo-tridentate 2,6 diformilpyiridine (DFP) exo-bidentate diamminobipyridiyl ligand (DAB) 5-coordinated Zn(II) (sale triflouroacetatato) reversibile imine formation reversible coordination

Carica: 12+ Controioni: 12TFA

After 2 days 90°C, MeOH NMR, mass spectrometry (ESI)

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[M-3TFA]3+ [M-4TFA]4+ [M-5TFA]5+

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6 Zn(II) bound to one bipy and one dimminopyridine (in the solid state 6th position occupied by triluoroacetate (TFA); S6 symmetry p-p stacking ech bipy between 2 phenols 3.61-3.66 Å; 12+

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NaBH4, EDTA

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Nodi Molecolari e Links

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https://www.youtube.com/watch?v=voihgqHlU_4