1. 1 Cyclic Tetranuclear and Hexanuclear Palladium(II) Complexes and Their Host-guest Chemistry Judith A. Walmsley,* Shourong Zhu, Antonio Matilla, Tiffanee G. Donowick, Jessica E. Cramp, Jose Manuel Tercero, and Tatyana Dalrymple Inorg. Chem. 2007, 46, 9945-9953

2. 2 Mirkin, 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.

3. 3 Selective Formation of Different Geometric Structures by Appropriate Choice of Corner and Bridging Units Kaiser, A.; Baeuerle, P. Top. Curr. Chem. 2005, 249, 127-201

4. 4 Extraction of Hydrophobic Species into a Water-Soluble Synthetic Receptor Hooley, R. J.; Van Anda, H. J.; Rebek, J., Jr. J. Am. Chem. Soc. 2007, 129, 13464-13473

5. 5 Molecular Necklace: Quantitative Self-Assembly of a Cyclic Oligorotaxane from Nine Molecules Whang, D.; Park, K.-M.; Heo, J.; Ashton, P.; Kim, K. J. Am. Chem. Soc. 1998, 120, 4899-4900

6. 6 Selective Formation of Different Geometric Structures by Appropriate Choice of Corner and Bridging Units Kaiser, A.; Baeuerle, P. Top. Curr. Chem. 2005, 249, 127-201

7. 7 Structure of Guanine, Guanosine, and Guanosine 5’-monophosphate (guanosine 5’-monophosphate) Walmsley, J. A. et al. Inorg. Chim. Acta 2004, 357, 411-420

8. 8 Proposed Coordination Process of Pd(en) 2+ with 5’GMP Walmsley, J. A. et al. Inorg. Chim. Acta 2004, 357, 411-420

9. 9 Figure 1. Structure of [Pd(en)(5’GMP)] 4 Pd(en)-5’GMP System Na 2 (5’GMP) 8.20 5.95 8.55 6.55 AA’BB’ multiplet singlet

10. 10 Figure 2. 1 H NMR spectra in D 2 O at pD 5.4 and 25 °C; (A) [Pd(en)-(5’GMP)] 4 (20 mM total Pd(II)); (B) mixture of [Pd(en)(5’GMP)] 4 and {-[Pd(en)(5’GMP)] 6 -DSS} (20 mM DSS and 20 mM total Pd(II)); ‘r’ stands for hexamer host-guest complex, ‘u’ stands for free guest ion. [Pd(en)(5’GMP)] 4 with DSS Guest Sodium 3-(trimethylsilyl)-1-propanesulfonate (DSS) -2.76 β-(CH 2 ) 1.19, 1.09 ppm (Δδ=0.4) γ-(CH 2 ) -0.91, -1.06 ppm (Δδ=1.4)

11. 11 Figure 4. Determination of Pd(en)(5’GMP)/DSS ratio in D 2 O at pD 5.4 by 1 H NMR integrated intensity of the H1’ of host [Pd(en)(5’GMP)] 6 and methyl protons of guest DSS; 10 mM total Pd(II) plus variable amounts of DSS. Determined Pd(en)(5’GMP)/DSS ratio by 1 H NMR slope = 5.9 ± 0.4, 6.0 ± 0.3

12. 12 Figure 3. 31 P NMR of 30 mM Pd(en)(5’GMP) in D 2 O (30 mM total Pd-(II)) with two different concentrations of DSS, pD 5.5; single line at 1.65 ppm is tetramer and two lines at 1.35-1.45 ppm are hexamer with DSS guest. 31 P NMR of Pd(en)(5’GMP)/DSS in D 2 O tetramer hexamer

13. 13 Nuclear Overhauser Effect SpectroscopY American physicist Albert Overhauser who hypothesized it in the early 1950s. The phenomenon was demonstrated by C. P. Slichter and T. R. Carver in 1953. Nuclear Overhauser Effect (NOE) arises throughout radio frequency saturation of one spin, the effect causes the perturbation via dipolar interactions with further nucleus spins. NOESY spectra provide information about protons that are 5 Angstroms or less apart in space. The information is through space and not through bond.

14. 14 Figure 5. Partial 1 H NOESY spectrum of [Pd(en)(5’GMP)] n (19 mM total Pd(II)) with 5 mM DSS in D 2 O at pD 5.7 and 25 °C. Partial 1 H NOESY Spectrum of [Pd(en)(5’GMP)] n with DSS Guest in D 2 O H1’ H8 H1’ H2’, H3’ methyl group

15. 15 Figure 6. (A) Proposed structure for the hexamer. The 5’GMP units are alternately pointing up and down around the ring. (B) Schematic drawing of [Pd(en)(5’GMP)] 6 with DSS guest. The oval represents the Pd(en)-(guanine) and the vertical solid, and wavy lines represent the ribose group. Water molecules may mediate H-bonding between phosphate anions and between phosphate and sulfonate groups. Proposed Structure for [Pd(en)(5’GMP)] 6 Hexamer with DSS Guest

16. 16 pH 4.0bonding of DSS was first observed pH 5.0-5.5reached a maximum pH 6.0decreasing pH 7.7only a small fraction of the DSS was bonded as host low pH pH 5.0-6.0 pH 6.5 Strong pH Dependence of Host-guest Formation

17. 17 Figure 7. 1 H NMR spectra of Pd(en)(5’GMP) (20 mM total Pd(II)) and t-butanol in D 2 O at pD 5.4 and 25 °C. The ‘u’ stands for the resonance from methyl protons of free t-butanol, and ‘r’ stands for methyl protons of guest or H8 and H1’ of hexamer. 1 H NMR Spectra of Pd(en)(5’GMP) with t-Butanol Guest in D 2 O Pd / t-butanol ratio is 5.9 ± 0.7

18. 18 1 H NOESY Spectrum of [Pd(en)(5’GMP)] n with t-Butanol Guest in D 2 O H1’ H8 t-BuOH methyl u r

19. 19 Figure 8. 1 H NMR resonances of i-butanol as guest in [Pd(en)(5’GMP)] 6 in D 2 O at pD 5.4 and 26 °C; (20 mM total Pd(II) and 10 mM total i-butanol). 1 H NMR Spectra of Pd(en)(5’GMP) with iso-butanol Guest in D 2 O iso-butanol heptet two doublets equal intensity J = 7.0 Hz r r r u u H8 H1’ u

20. 20 1 H NMR Spectrum of Pd(en)(5’GMP) with 2-Propanol Guest in D 2 O r u u r 2-PrOH r 2-PrOH u H8 H1’

21. 21 1 H NMR Spectrum of Pd(en)(5’GMP) with TMS Guest in D 2 O tetramethylsilane (TMS)

22. 22 Crystal Structure of [Pd(dapol)Cl 2 ] Figure 10. ORTEP drawing of [Pd(dapo)Cl 2 ] with the atomic numbering scheme; displacement ellipsoids are shown at the 50% level. Table 4. Selected Bond Lengths (Å) and Angles (deg) for [Pd(dapol)Cl 2 ] 1,3-diamino-2-propanol (dapol)

23. 23 Figure S12. Packing diagram of [Pd(dapol)Cl 2 ]; Color code: Pd (green), Cl (yellow), C (black), N (blue), O (red), H (white). Packing Diagram of [Pd(dapol)Cl 2 ]

24. 24 Figure 9. 1 H NMR spectra in D 2 O at 25 °C. (A) 25 mM Pd(dapol)-(5’GMP), pD 5.4 (25 mM total Pd(II)); (B) mixture of (A) and [Pd(dapol)-(5’GMP)] 6 -2-PrOH (20 mM total Pd(II), 1.5 mM 2-PrOH), pD 5.8. ‘react’ refers to the host-guest complex. 1 H NMR Spectra of Pd(dapol)(5’GMP) with 2-Propanol Guest in D 2 O 1,3-diamino-2-propanol (dapol)

25. 25 Chemical Shifts of Methyl Protons of Guests in [Pd(diamine)(5’GMP)] n Table 2. Chemical Shifts of Methyl Protons of Guests in [Pd(diamine)(5’GMP)] n a TSP = Sodium 3-(trimethysilyl)propionate-d 4 DSS = Sodium 3-(trimethylsilyl)-1-propanesulfonate TMS = Tetramethylsilane

26. 26 Table 3. K’ assoc and Thermodynamic Parameters of [Pd(en)(GMP)] 6 Host-Guest Complexes at 26 °C Association Constants of [Pd(en)(GMP)] 6 Host-Guest Complexes

27. 27 Conclusions 1.Upon the introduction of a small organic molecule with hydrophobic interaction sites, the tetramers spontaneously expanded to form a hexamer with one guest molecule strongly incorporated into the central cavity. 2.We feel that the ease with which the tetramer expanded to the hexamer might be related to unfavorable steric interactions of the 5’GMP at the N7-Pd-N7 corners in the tetramer, rendering the expansion in the presence of a templating agent enegetically favorable. 3.The guests can be cationic, anionic, or neutral with a high degree of hydrophobic character. They bind strongly to the host in a 1:1 mole ratio, are in slow chemical exchange with uncomplexed guest molecules, and exhibit very large upfield chemical shifts (2.5-3.0 ppm) in the NMR spectra for the most highly affected protons.

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