1. 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,

2. 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. Newkome, G. R. et al. Chem. Rev. 1999, 99, 1689-1746.
Metallodendrimer
Newkome, G. R. et al. Chem. Rev. 1999, 99,

6. Metals as Branching Centers
Denti, G. et al. J. Am. Chem. Soc. 1992, 114,

7. Metals as Building Block Connectors
Puddephatt, R. J. et al. Organometallics 1995, 14,

8. Fréchet, J. M. et al. Chem. Mater. 1998, 10, 30-38.
Metals as Cores
Fréchet, J. M. et al. Chem. Mater. 1998, 10,

9. Metals as Termination Groups (Surface Functionalization)
Lemo, J.; Heuze, K.; Astruc, D. Org. Lett. 2005, 7,

10. Metals as Structural Auxiliaries
Kaneda, K. J. Am. Chem. Soc. 2004, 126,

11. Supramolecular Coordination Chemistry
Hydrogen bonding
Metal-ligand coordination
π-π stacking
Eletrostatic interactions
van der Waals forces
Hydrophobic interactions
Hydrophilic interactions
etc.
Mirkin, C. A. et al. Angew. Chem. Int. Ed. 2001, 40,

12. Supramolecular Assembly of Polyhedra
Stang, P. J.; Olenyuk, B. Acc. Chem. Res. 1997, 30,

13. Self-Assembly of Rhomboidal and Hexagonal, “Snowflake-Shaped”
Metallodendrimers.

14. Angular Dendritic Donor Precursors
Synthesis of [G0]-[G3] 120o
Angular Dendritic Donor Precursors
Sonogashira coupling
acylation
hydrolysis
etherification
在120度ligand的前驅物合成
作者選用3,5-dibromo-phenol 1號Compound
兩個bromo呈現夾角為120度
先作一個acylation利用acyl group作一個保護基形成2號Compound
兩個bromo進行sonogashira C-C coupling reaction形成3號Compound有兩個pyridyl group
ester group 經過hydrolysis(水解)去保護基形成4號Compound
然後再進行etherification(醚化) SN2的反應形成Compound 5a-5d

15. Structures of [G0]-[G3] 120o Angular Donor Precursors 5a-d

16. Self-Assembly of Rhomboidal Metallodendrimers 7a-d
31P{1H} NMR
δ14.6 ppm (-6.4 ppm)
1JPt-P= (-177 Hz)
96-99%
Hα Hβ 5a 5b 5c 5d
Hα Hβ
7a 9.35,
7b 9.36,
7c 9.37,
7d 9.36,

17. Structures of [G0]-[G3]-Rhomboidal Metallodendrimers 7a-d

18. Calculated and Experimental ESI-MS Spectra of
[G0]-[G2]-Rhomboidal Metallodendrimers 7a-c
[M-2NO3] [M-3NO3] [M-2NO3] [M-3NO3]3+ [M-2NO3] [M-3NO3]3+
C130H172N8O14P8Pt C158H196N8O18P8Pt 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 %

19. Calculated and Experimental ESI-FT-ICR-MS
Spectra of [G3]-Rhomboidal Metallodendrimer 7d
C326H340N8O42P8Pt4
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%)
P 31(100.0%)
Pt 192(0.8%) 194(32.9%)
195(33.8%) 196(25.3%)
198 (7.2%)

20. [G0]-Rhomboidal Metallodendrimer 7a
Crystal Structure of
[G0]-Rhomboidal Metallodendrimer 7a
3.3 nm long
2.8 nm wide

21. [G1]-Rhomboidal Metallodendrimer 7b
Crystal Structure of
[G1]-Rhomboidal Metallodendrimer 7b
4.2 nm long
2.8 nm wide

22. Wireframe Representation of the Crystal Structure
of Metallodendrimer 7a and 7b
1.3 nm
2.3 nm

23. Self-Assembly of Hexagonal, “Snowflake-Shaped” Metallodendrimers 10a-d and 11a-d

24. Partial 1H NMR spectra of 5d, 10d and 11dβ α

25. 31P NMR Spectra of [G3]-Hexagonal Metallodendrimer 10d and 11d
Compaired with 8
δ (-6.5 ppm)
Δ1J PPt = -131 Hz
Compaired with 9
δ (-6.4 ppm)
Δ1JPPt = -150 Hz

26. Calculated and Experimental ESI-FT-ICR-MS Spectra
of [G0]-[G2]-Hexagonal Metallodendrimers 10a-c
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%)
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%)
C282H348F36N12O42P24Pt12S C366H420F36N12O54P24Pt12S C534H564F36N12O78P24Pt12S12

27. Full ESI-FT-ICR Mass Spectrum of [G1]-Hexagonal Metallodendrimer 10b

28. Calculated and Experimental ESI-FT-ICR-MS Spectra
of [G0]-[G2]-Hexagonal Metallodendrimers 11a-c
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%)
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%)
C390H516F36N12O42P24Pt12S C474H588F36N12O54P24Pt12S C642H732F36N12O78P24Pt12S12

29. Space-Filling Models of Hexagonal Metallodendrimers 10d and 11d
Optimized with the MM2 Force-Field Simulation

30. Conclusions
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.
Metallodendrimers having nonplanar hexagonal cavities with different internal radii of approximately 1.6, 2.5, and 2.9 nm have been obtained.
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.

31. Mechanism of acylation

32. Mechanism of hydrolysis
Hydrolysis of Esters
Base-catalysed hydrolysis
Mechanism of hydrolysis
Step 1 : Reversible attack at carbonyl carbon by base
Step 2 : Protion transfer

33. Mechanism of Sonogashira Coupling
organic-chemistry.org

34. Mechanism of Heck Coupling
organic-chemistry.org

35. Mechanism of Suzuki Coupling
organic-chemistry.org