1. Dougherty, D. A., Science, 1996, 271,163.

2. Red = most negative electrostatic potentials (most basic regions)
Blue = most positive electrostatic potentials (most acidic regions)
Dougherty et al., Proc. Natl. Acad. Sci. USA, Vol. 93, pp –10571, October 1996
Chemistry

3. OR
p base
p acid
Burini; Fackler; Omary; Staples et al. J. Am. Chem. Soc. 2000, 122,
TRHg

4. DFT Calculations of Trinuclear Complexes
[Hg(C6F4)]3
[Au(bzim)]3
Electrost. Pot. (a.u.)

5. Electrostatic Potential Surfaces
[Hg(C6F4)]3
green = positive
[Au(bzim)]3
red = negative
p-Electrostatic interaction

6. ADF Calculations
{[Au(carb)]3}2
DIMER
Green= positive
Red=negative

7. SUPER WHOPPER!!
p base
p acid
p base

8. SUPRAMOLECULAR CHAIN ASSEMBLIES
p base
p acid
p base
p acid
Burini; Fackler; Omary; Staples et al. J. Am. Chem. Soc. 2000, 122,

9. Solid-state example: p acid p base p acid p base p acid
Phosphorescence at RT in the solid-state!!
= 568 ± 8 ms (RT)

10. Complexation of [Hg(o-C6F4)]3, 1, with aromatic hydrocarbons… RGB bright phosphorescent emissions for the 1:1 solid adducts
Omary; Kassab; Haneline; Elbjeirami; Gabbai Inorg. Chem. 2003, 42,

11. Au3(carb)3.octafluoronaphthalene
t = 3.6 ms
p acid
p base
p acid
p base

12. R= e-withdrawing (e.g., CF3)
makes it more of a p acid
R= e-releasing (e.g., Me; i-Pr; t-Bu)
 makes it more of a p base
M= Cu; Ag; Au
Metal effect??…

13. red=most negative= strong p base; blue=most positive= strong p acid;
DFT-calculated electrostatic potentials mapped on the electron density surfaces of M3Pz3 complexes.
Color code:
red=most negative= strong p base;
blue=most positive= strong p acid;
Yellow= neutral/weak p base
green=neutral/weak p acid
Cu3Pz3 Ag3Pz3, Au3Pz3
Pz ligands here have R=Me groups on them all

15. All strong p acids
But given previous slide we think that the Ag3 compound would be the strongest p acid
Calculations done by Alex Gonser, as a CHEM5610 classroom project last year.

16. SUMMARY
Ligand effect:
R= e-withdrawing (e.g., CF3)
makes it more of a p acid
R= e-releasing (e.g., Me; i-Pr; t-Bu)
 makes it more of a p base
Metal effect:
Relative p basicity: Au>Cu>Ag
Relative p acidity: Ag>Cu>Au
M= Cu; Ag; Au
If you want to react with naphthalene (p base), what would you choose for R and M to form an acid-base adduct?

17. Maha Eldabaja (4610 student here doing research in the Omary group)…
Maha Eldabaja (4610 student here doing research in the Omary group)….just got crystals of an adduct for [Ag(3,5-(CF3)2Pz)]3 with naphthalene and found that it has green emission, consistent with naphthalene phosphorescence

18. (let’s hear it for Maha!!)
Maha Eldabaja (4610 student here doing research in the Omary group)….just got crystals of an adduct for [Ag(3,5-(CF3)2Pz)]3 with naphthalene and found that it has green emission, consistent with naphthalene phosphorescence
(let’s hear it for Maha!!)
Chi2 :
Durbin Watson : 1.85
Z :
Pre-exp. 1 : ±1.638E+001
Lifetime 1 : E+004 ms ±6.652E+002
Offset : 26.5
t = 15.8 ± 0.7 ms