1 molecular catenation via metal-directed self-assembly andπ-donor/π-acceptor interactions:...
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Molecular Catenation via Metal-Directed Self-Assembly andπ-Donor/π-Acceptor Interactions: Efficient
One-Pot Synthesis, Characterization, and Crystal Structures of [3]Catenanes Based on Pd or Pt Dinuclear Metallocycles
Víctor Blanco, Marcos Chas, Dolores Abella, Carlos Peinador,* andJosé M. Quintela*
J. Am. Chem. Soc. 2007, 129, 13978-13986
Speaker: 黃仁鴻
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Synthesis of [n]Catenanes
1. π-Donor/π-Acceptor complexes
2. Hydrogen bond interactions
3. Anion templation
4. Metal complexation
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A Chemically-Switchable [2]Catenane
Figure 1. The [2]catenane 14+ and the translational isomers (2A4+ and 2B4+) of the [2]catenane 24+.
Balzani, V.; Credi, A.; Langford, S. J.; Raymo, F. M.; Stoddart, J. F.;Venturi, M. J. Am. Chem. Soc. 2000, 122, 3542.
a b c
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Amide-Based Interlocked Compounds
Leigh, D. A.; Venturini, A.; Wilson, A. J.; Wong, J. K. Y.; Zerbetto, F. Chem.-Eur. J. 2004, 10, 4960.
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Anion-Templated Assembly of a [2]Catenane
Sambrook, M.; Wisner, J. A.; Paul, R. L.; Cowley, A. R.; Szemes, F.; Beer,P. D. J. Am. Chem. Soc. 2004, 126, 15364.
Figure 2. Strategy for assembly of [2]-catenanes via anion templation.
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Figure 3. Synthesis of a catenane using an octahedral metal atom and three bidentate chelates: construction principle.
Chambron, J.-C.; Collin, J.-P.; Heitz, V.;Jouvenot, D.; Kern, J.-M.; Mobian, P.; Pomeranc, D.; Sauvage, J.-P. Eur. J. Org. Chem. 2004, 1627.
Catenanes Built Around Octahedral Transition Metals
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Synthesis of [n]Catenanes
1. π-Donor/π-Acceptor complexes
2. Hydrogen bond interactions
3. Anion templation
4. Metal complexation
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Structures of Molecular ComponentsUsed in This Work
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• Dinuclear molecular squares 3a,b• Pseudorotaxanes
• [3]-Catenanes (BPP34C10)2-(3a,b)
• [3]-Catenanes (DB24C8)2-(3a,b)
• [3]-Catenanes (DN38C10)2-(3a,b)
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Synthesis of Dinuclear Molecular Squares 3a,b
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1H NMR Spectrum of 3a·4OTf·4PF6
a
a
8.99 ppm
△8.91 ppm
8H 8H
8H4H
8H
8H
8H
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13C NMR Spectrum of 3a·4OTf·4PF6
DEPT-135
CH2
CH2
C C
a
bcd
i
g
e
f
h
CHCHCH CH
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HSQC Spectrum of 3a·4OTf·4PF6
a
bcd
i
g
e
f
h
i
Heteronuclear Single Quantum Coherence1H-13C 1J
1H NMR
13C NMR
a
a
h
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COSY Spectrum of 3a·4OTf·4PF6
a
bcd
i
g
e
f
h
1H NMR
1H NMR
COrrelation SpectroscopY1H-1H 3J
h
i
i
h
b
a
a
b
g
g
e f
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HMBC Spectrum of 3a·4OTf·4PF6
a
bcd
i
g
e
f
h
13C NMR
1H NMR
Heteronuclear Multiple Bond Coherence 1H-13C 1J, 2J, 3J
g
fb
a
a
c
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a b154.0 ppm
126.2 ppm
a
bc
c144.9 ppm
Δδ=1.6 ppmΔδ=3.1 ppm
Δδ=3.5 ppm
fa b e
g
h
i
d
fe
g
h
a
bcd
i
g
e
f
h
1H & 13C NMR Spectra of 3a·4OTf·4PF6
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1H NMR Spectra of 1·2PF6 and 2aat Different Concentrations
10 mM
5 mM
2.5 mM
0.5 mM
1·2PF6
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• Dinuclear molecular squares 3a,b• Pseudorotaxanes
• [3]-Catenanes (BPP34C10)2-(3a,b)
• [3]-Catenanes (DB24C8)2-(3a,b)
• [3]-Catenanes (DN38C10)2-(3a,b)
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Rotaxane
http://en.wikipedia.org/wiki/Rotaxane
http://www.catenane.net/home/rotcatintro.html
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Crystal Structure of Pseudorotaxane Complex between 1·2PF6 and DB24C8
a 2.52 Å 149° b 2.26 Å 167° c 2.21 Å 167° d 2.37 Å 168°
[H…O] distances [C-H…O] angle
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1H NMR Spectrum of DB24C8-1·2PF6 Pseudorotaxane
g
f
Δδ=0.40 ppm
Δδ=0.30 ppm
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• Dinuclear molecular squares 3a,b• Pseudorotaxanes
• [3]-Catenanes (BPP34C10)2-(3a,b)
• [3]-Catenanes (DB24C8)2-(3a,b)
• [3]-Catenanes (DN38C10)2-(3a,b)
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Crystal Structure of The [3]Catenane (BPP3410)2-(3a)
3.83 Å
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Partial 1H NMR Spectra of Metallocycle 3a and (BPP34C10)2-(3a)
Figure 2. Partial 1H NMR (CD3CN, 500 MHz) spectra of metallocycle 3a(top) and (BPP34C10)2-(3a) at 237 K (bottom).
Δδ= -0.7ppm
Δδ= -0.7ppm
Δδ= -0.1ppm
Δδ= -0.3ppm
ab
e
f
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Electrospray Ionization MassSpectrometry
Figure 4. Observed (top) and theoretical (bottom) isotopic distribution forthe fragment [(BPP34C10)2-(3b) - 3PF6]+3.
Isotope %
H 1(100.0%)C 12(98.9%) 13(1.1%)N 14(99.6%) 15(0.4%)O 16(99.8%) 18(0.2%)F 19(100.0%)P 31(100.0%)Pt 192(0.8%) 194(32.9%) 195(33.8%) 196(25.3%) 198 (7.2%)
C102H132F30N12O20P5Pt2
987.0
987.0
[(BPP34C10)2-(3b) - 3PF6]+3
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• Dinuclear molecular squares 3a,b• Pseudorotaxanes
• [3]-Catenanes (BPP34C10)2-(3a,b)
• [3]-Catenanes (DB24C8)2-(3a,b)
• [3]-Catenanes (DN38C10)2-(3a,b)
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1H NMR Spectra of (DB24C8)2-(3a)
Figure 5. Partial 1H NMR (CD3CN, 298 K) spectra of (a) metallocycle 3a (5 mM), (b) 3a (5 mM) + DB24C8 (10 mM), and (c) 3a (5 mM) + DB24C8(20 mM).
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Crystal Structure of [3]Catenane (DB24C8)2-(3a)
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Reversible Catenation of (DB24C8)2-(3a)
Figure 6. 1H NMR (CD3CN, 300 MHz, 298 K) spectra of (a) metallocycle 3a (5 mM), (b) solution (a) + DB24C8 (20 mM), (c) solution (b) + KPF6 (20 mM), (d) solution (c) + 18C6 (20 mM).
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• Dinuclear molecular squares 3a,b• Pseudorotaxanes
• [3]-Catenanes (BPP34C10)2-(3a,b)
• [3]-Catenanes (DB24C8)2-(3a,b)
• [3]-Catenanes (DN38C10)2-(3a,b)
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Crystal Structure of (DN38C10)2-(3a)
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Crystal Structure of (DN38C10)2-(3b)
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Conclusions1. Ligand 1 2PF6 threads through the cavity of ‧ DB24C8
to generate a [2]pseudorotaxane that is stabilized principally by hydrogen-bonding interactions.
2. The solid-state structure of catenane (DB24C8)2-(3a) revealed that the Pd(en) corners of metallocycle are capped with two additional polyether cyclophanes to form a supramolecular complex composed of eight components.
3. The catenation process of (DB24C8)2-(3a) can be switched off and on in a controllable manner by successive addition of KPF6 and 18-crown-6.
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Conclusions(continued)
4. The reported catenanes are composed of a dinuclear m
olecular square bridged by ligand 1 2PF‧ 6 interpenetrated by two polyether macrorings.
5. X-ray crystallography in combination with NMR studies showed that π-πstacking and [C-H…π] interactions in addition to [C-H…O]hydrogen bonds are the noncovalent forces that stabilize the [3]catenanes.
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