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Coordination-Driven Self-Assembly of Metallodendrimers Possessing Well-Defined and Controllable Cavities as Cores. Hai-Bo Yang,* Adam M. Hawkridge, Songping D. Huang, Neeladri Das, Scott D. Bunge, David C. Muddiman, and Peter J. Stang*. J. Am. Chem. Soc. 2007 , 129 , 2120-2129. - PowerPoint PPT Presentation
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Coordination-Driven Self-Assembly of Metallodendrimers Possessing Well-Defined and C
ontrollable Cavities as Cores
Hai-Bo Yang,* Adam M. Hawkridge, Songping D. Huang, Neeladri Das,Scott D. Bunge, David C. Muddiman, and Peter J. Stang*
J. Am. Chem. Soc. 2007, 129, 2120-2129.
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The Dendritic Structure
Host-guest chemistry
Material science
Membrane chemistry
Catalysis
Stoddart, J. F. et al. Prog. Polym. Sci. 1998, 23, 1-56.
3
“Convergent” Dendrimer Growth
Stoddart, J. F. et al. Prog. Polym. Sci. 1998, 23, 1-56.
4
“Divergent” Dendrimer Growth
Stoddart, J. F. et al. Prog. Polym. Sci. 1998, 23, 1-56.
5
Metallodendrimer
Newkome, G. R. et al. Chem. Rev. 1999, 99, 1689-1746.
6
Metals as Branching Centers
Denti, G. et al. J. Am. Chem. Soc. 1992, 114, 2944-2950.
7
Metals as Building Block Connectors
Puddephatt, R. J. et al. Organometallics 1995, 14, 1681-1687.
8
Metals as Cores
Fréchet, J. M. et al. Chem. Mater. 1998, 10, 30-38.
9Lemo, J.; Heuze, K.; Astruc, D. Org. Lett. 2005, 7, 2253-2256.
Metals as Termination Groups (Surface Functionalization)
10Kaneda, K. J. Am. Chem. Soc. 2004, 126, 1604-1605.
I I + RPd complex
KOAc, 100oC, ArI
R+
R
R
major minor
Metals as Structural Auxiliaries
11Mirkin, C. A. et al. Angew. Chem. Int. Ed. 2001, 40, 2022-2043.
Supramolecular Coordination Chemistry
Hydrogen bonding
Metal-ligand coordination
π-π stacking
Eletrostatic interactions
van der Waals forces
Hydrophobic interactions
Hydrophilic interactions
etc.
12Stang, P. J.; Olenyuk, B. Acc. Chem. Res. 1997, 30, 502-518
Supramolecular Assembly of Polyhedra
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Self-Assembly of Rhomboidal andHexagonal, “Snowflake-Shaped”
Metallodendrimers.
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Synthesis of [G0]-[G3] 120o
Angular Dendritic Donor Precursors
acylation
Sonogashira coupling
hydrolysis etherification
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Structures of [G0]-[G3] 120o
Angular Donor Precursors 5a-d
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Self-Assembly of Rhomboidal Metallodendrimers 7a-d
Hα Hβ
5a 8.60 7.39-7.455b 8.60 7.33-7.445c 8.60 7.31-7.425d 8.60 7.31-3.42
Hα Hβ
7a 9.35, 8.72 7.597b 9.36, 8.70 7.597c 9.37, 8.68 7.597d 9.36, 8.65 7.58
96-99%
31P{1H} NMRδ14.6 ppm (-6.4 ppm)1JPt-P=2707.7 (-177 Hz)
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O
N NPt Pt
PEt3
Et3P
Et3P
PEt3
Pt PtN N
PEt3
Et3P
Et3P
PEt3
O
OO
OO
O
O
O O
O
O
O
O
O
O
O O
O O
O
O
OO
O
O
O
O
O
O
O
N NPt Pt
PEt3
Et3P
Et3P
PEt3
Pt PtN N
PEt3
Et3P
Et3P
PEt3
O
OO
OO
OO
O O
O O
O O
Structures of [G0]-[G3]-Rhomboidal Metallodendrimers 7a-d
O
N NPt Pt
PEt3
Et3P
Et3P
PEt3
Pt PtN N
PEt3
Et3P
Et3P
PEt3
O
OO
O O
O
N NPt Pt
PEt3
Et3P
Et3P
PEt3
Pt PtN N
PEt3
Et3P
Et3P
PEt3
O
7a
7b
7c
7d
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Calculated and Experimental ESI-MS Spectra of [G0]-[G2]-Rhomboidal Metallodendrimers 7a-c
[M-2NO3]2+ [M-3NO3]3+ [M-2NO3]2+ [M-3NO3]3+ [M-2NO3]2+ [M-3NO3]3+ C130H172N8O14P8Pt4 C158H196N8O18P8Pt4 C214H244N8O26P8Pt4
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%)P 31(100.0%)Pt 192(0.8%) 194(32.9%) 195(33.8%) 196(25.3%) 198 (7.2%)
Isotope %
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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%)P 31(100.0%)Pt 192(0.8%) 194(32.9%) 195(33.8%) 196(25.3%) 198 (7.2%)
Calculated and Experimental ESI-FT-ICR-MSSpectra of [G3]-Rhomboidal Metallodendrimer 7d
C326H340N8O42P8Pt4
Isotope %
20
3.3 nm long2.8 nm wide
Crystal Structure of[G0]-Rhomboidal Metallodendrimer 7a
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Crystal Structure of[G1]-Rhomboidal Metallodendrimer 7b
4.2 nm long2.8 nm wide
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Wireframe Representation of the Crystal Structureof Metallodendrimer 7a and 7b
2.3 nm
1.3 nm
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Self-Assembly of Hexagonal, “Snowflake-Shaped” Metallodendrimers 10a-d and 11a-d
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Partial 1H NMR spectra of 5d, 10d and 11d
αβ
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31P NMR Spectra of [G3]-Hexagonal Metallodendrimer 10d and 11d
Compaired with 8δ (-6.5 ppm)
Δ1J PPt = -131 Hz
Compaired with 9δ (-6.4 ppm)
Δ1JPPt = -150 Hz
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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%)S 32(95.0%) 33(0.8%) 34(4.2%)Pt 192(0.8%) 194(32.9%) 195(33.8%) 196(25.3%) 198 (7.2%)
Calculated and Experimental ESI-FT-ICR-MS Spectraof [G0]-[G2]-Hexagonal Metallodendrimers 10a-c
C282H348F36N12O42P24Pt12S12 C366H420F36N12O54P24Pt12S12 C534H564F36N12O78P24Pt12S12
Isotope %
27
Full ESI-FT-ICR Mass Spectrum of [G1]-Hexagonal Metallodendrimer 10b
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Calculated and Experimental ESI-FT-ICR-MS Spectraof [G0]-[G2]-Hexagonal Metallodendrimers 11a-c
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%)S 32(95.0%) 33(0.8%) 34(4.2%)Pt 192(0.8%) 194(32.9%) 195(33.8%) 196(25.3%) 198 (7.2%)
C390H516F36N12O42P24Pt12S12 C474H588F36N12O54P24Pt12S12 C642H732F36N12O78P24Pt12S12
Isotope %
29
Space-Filling Models of Hexagonal Metallodendrimers 10d and 11d
Optimized with the MM2 Force-Field Simulation
30
Conclusions
1. This approach makes it possible to prepare a variety of metallodendrimers with well-defined and controlled cavities as cores through the proper choice of subunits with predefined angles and symmetry, which enriches the library of different-shaped cavity-cored metallodendrimers.
2. Metallodendrimers having nonplanar hexagonal cavities with different internal radii of approximately 1.6, 2.5, and 2.9 nm have been obtained.
3. We have demonstrated that highly convergent synthetic protocols of appropriate predetermined building blocks allow the rapid construction of novel cavity-cored metallodendrimers. The shape of the cavities of the supramolecular dendrimers can be rationally designed to be either a rhomboid or a hexagon.
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Acylation
ROHO
O O
RO
O
Mechanism of acylation
O
O O
ROH
O
O O
OHR
RO
O
H
+O
O
1. ice
2. baseRO
O
+ H-baseO
O+
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ROR'
O+ OH R
O
O+ R'OH
Hydrolysis of Esters
ROR'
O
OH
ROR'
O
HOR
OH
O+ R'O
Base-catalysed hydrolysis
Mechanism of hydrolysisStep 1 : Reversible attack at carbonyl carbon by base
Step 2 : Protion transfer
ROH
O+ R'O R
O
O+ R'OH
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Mechanism of Sonogashira Coupling
organic-chemistry.org
34
Mechanism of Heck Coupling
organic-chemistry.org
35
Mechanism of Suzuki Coupling
organic-chemistry.org
36