Dougherty,%20D.%20A.,%20Science,%201996,%20271,163.

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Dougherty, D. A., Science, 1996, 271,163.
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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. 1056610571, October 1996 Chemistry
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OR
p base
p acid
Burini Fackler Omary Staples et al. J. Am.
Chem. Soc. 2000, 122, 11264-11265.
TRHg
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DFT Calculations of Trinuclear Complexes
Hg(C6F4)3
Au(bzim)3
Electrost. Pot. (a.u.) -0.0300
0.0300
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Electrostatic Potential Surfaces
Hg(C6F4)3 green positive Au(bzim)3 red
negative
p-Electrostatic interaction
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ADF Calculations
Au(carb)32 DIMER
Green positive Rednegative
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SUPER WHOPPER!!
p base
p acid
p base
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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.
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Solid-state example
p acid
p base
p acid
p base
p acid
Phosphorescence at RT in the solid-state!!

• 568 8 ms (RT)

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Complexation of Hg(o-C6F4)3, 1, with aromatic
hydrocarbons RGB bright phosphorescent
emissions for the 11 solid adducts
Omary Kassab Haneline Elbjeirami Gabbai
Inorg. Chem. 2003, 42, 2176-2178.
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Au3(carb)3.octafluoronaphthalene
t 3.6 ms
p acid
p base
p acid
p base
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• 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??
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DFT-calculated electrostatic potentials mapped
on the electron density surfaces of M3Pz3
complexes. Color code redmost negative strong
p base bluemost positive strong p acid
Yellow neutral/weak p base greenneutral/weak
p acid
Cu3Pz3 Ag3Pz3, Au3Pz3
Pz ligands here have RMe groups on them all
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(No Transcript)
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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.
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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
AugtCugtAg Relative p acidity AggtCugtAu
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?
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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
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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 (lets hear it
for Maha!!)
Chi2 1.032 Durbin Watson 1.85 Z
374.2 Pre-exp. 1 825.2 1.638E001 Lifetime
1 1.575E004 ms 6.652E002 Offset 26.5
t 16 ms