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

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. 10566–10571, October 1996 Chemistry

OR p base p acid Burini; Fackler; Omary; Staples et al. J. Am. Chem. Soc. 2000, 122, 11264-11265. TRHg

DFT Calculations of Trinuclear Complexes [Hg(C6F4)]3 [Au(bzim)]3 Electrost. Pot. (a.u.) -0.0300 0.0300

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

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

SUPER WHOPPER!! p base p acid p base

SUPRAMOLECULAR CHAIN ASSEMBLIES p base p acid p base p acid Burini; Fackler; Omary; Staples et al. J. Am. Chem. Soc. 2000, 122, 11264-11265.

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

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, 2176-2178.

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

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??…

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

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.

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?

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

(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 : 1.032 Durbin Watson : 1.85 Z : 374.2 Pre-exp. 1 : 825.2 ±1.638E+001 Lifetime 1 : 1.575E+004 ms ±6.652E+002 Offset : 26.5 t = ~ 16 ms