From the Bottom Up: Hydrogen Bonding in Ionic Liquids 6/19/2014 Olga Gorlova, Conrad Wolke, Joseph Fournier, Christopher Johnson and Mark Johnson.

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Presentation transcript:

From the Bottom Up: Hydrogen Bonding in Ionic Liquids 6/19/2014 Olga Gorlova, Conrad Wolke, Joseph Fournier, Christopher Johnson and Mark Johnson

Ionic Liquids Purely Ionic Salt Like Notably low vapor pressures o Large & Asymmetric Cation (EMIM + ) m (BF 4 ¯) n (EMIM + ) m (Cl¯) n (EMIM + ) m (Tf 2 N¯) n Liquids at Room Temperatures

ESI Needle Temperature Controlled Ion Trap Mounted to He Cryostat Ion Optics 2m Flight Tube Wiley- McLaren TOF Reflectron DC-Turning Quad MCP Detector Differential Aperture Skimmers Heated Capillary RF-Ion Guides Experimental Setup hv = cm -1 Collisional cooling in 3D Paul Trap -Pulsed He and N 2 gas Pulsed Valve Ions inIons out Paul Trap 10 K RF Cryogenic Ion Trap

ESI Needle Temperature Controlled Ion Trap Mounted to He Cryostat Ion Optics 2m Flight Tube Wiley- McLaren TOF Reflectron DC-Turning Quad MCP Detector Differential Aperture Skimmers Heated Capillary RF-Ion Guides Experimental Setup hv = cm -1 Room Temperature Ion Cold “Tagged” Ion Photofragment Absorption Evaporation

1-Ethyl-3-methylimidazolium (EMIM + ) (BF 4 ¯) (EMIM + ) m (BF 4 ¯) n

% Abs Photon Energy / cm -1 Bulk FT-IR (EMIM + ) (BF 4 ¯) Et/Me CH stretches Ring CH stretches

% Abs Photon Energy / cm -1 Bulk FT-IR (EMIM + ) (BF 4 ¯) Et/Me stretches Ring CH ip bends Et/Me bends Ring CH stretches Ring stretches EMIM + (calc) Calc. Int. (EMIM + ) (BF 4 ¯) * 2 PEAKS? Red shift caused by H-bond?

Pred. Yield % Abs. EMIM Photon Energy / cm -1 Bulk FT-IR Et/Me stretches Ring CH ip bends Et/Me bends Ring CH stretches Ring stretches EMIM + (calc) Calc. Int. * Isolated (EMIM + ) Spectrum Same Red Shifted Peak in Bare Ion * Anion Contribution ?

Pred. Yield % Abs. ν3ν3 ν1ν1 11 BF 4 ‾ EMIM Photon Energy / cm -1 Bulk FT-IR Et/Me stretches Ring CH ip bends Et/Me bends Ring CH stretches Ring stretches EMIM + (calc) Calc. Int. * * Low Energy Band Broadened asymmetric B-F stretch C.J. Johnson, et. al, J. Chem. Phys. 139, (2013)

Pred. Yield % Abs. ν3ν3 ν1ν1 11 BF 4 ‾ EMIM Photon Energy / cm -1 (2,1) Bulk FT-IR Et/Me stretches Ring CH ip bends Et/Me bends Ring CH stretches EMIM + (calc) Calc. Int. (EMIM + ) 2 (BF 4 ¯) Spectral response to assembly? C.J. Johnson, et. al, J. Chem. Phys. 139, (2013)

Deuteration Isolate the C (2) H Photon Energy / cm -1 C (2) D ip bend C (2) D Pred. Yield Ring CH ip bends Et/Me bends Ring stretches Et/Me stretches Ring CH stretches

[d (2) -EMIM][BF 4 ] bulk Predissociation Yield Photon Energy / cm -1 d (2) -EMIM + d (2) -(2,1) EMIM + (2,1) Bare C (4,5) H stretches Bare C (4,5) H stretches C (2) D stretch (EMIM + ) 2 (BF 4 ¯) Deuterated Et/Me stretches Ring CH stretches C.J. Johnson, et. al, J. Chem. Phys. 139, (2013)

Forcing the Hydrogen Bond Cl¯  Should strengthen the cation-anion interaction  Still a spherical anion  Will simplify the problem

Predissociation Yield Photon Energy (cm -1 ) Hydrogen Bonding x5 (EMIM + ) (EMIM + ) 2 (BF 4 ¯) (EMIM + ) 2 (Cl¯) Ring CH ip bends Et/Me bends Ring stretches Et/Me stretches Ring CH stretches

Photon Energy (cm -1 ) Predissociation Yield ν C(2)D ν C(2)H (2,1) (1,0) x5 (EMIM + ) 2 (Cl¯) Deuterated

Ionic Liquids BF 4 ¯ Anion Effects Tf 2 N¯ Cl¯

Ring CH ip bends N-shuttle C-F/C-S stretch S-O stretch Et/Me bends Ring Stretches Et/Me stretches Ring CH Stretches (1,0) (0,1) (1,2) (EMIM + ) 1 (Tf 2 N¯) 2 Predissociation Yield Photon Energy (cm -1 )

Predissociation Yield Photon Energy (cm -1 ) H-Bonding (EMIM + ) (Cl¯) 2 (EMIM + ) (Tf 2 N¯) 2 ~0 Is it Hydrogen Bonding? Deuterated Spectra

Conclusions A true hydrogen bond can be observed with the Cl¯, while Tf 2 N¯ and BF 4 ¯ have minimal hydrogen bonding character. Deuteration serves to isolate the acidic H- bonding position from other C-H stretches and Fermi resonances to better study the nature of the hydrogen bonding at the acidic position.

Acknowledgements Conrad Wolke Joseph Fournier Chris Johnson Patrick Kelleher Steph Craig Gary Weddle Mark Johnson RG07 – Protonated Water Clusters

Pred. Yield % Abs. ν3ν3 ν1ν1 11 BF 4 ‾ EMIM + (2,1) Photon Energy / cm -1 (1,2) x10 x5 * 10 BF 4 ‾ Bulk FT-IR Et/Me stretches Ring CH ip bends Et/Me bends Ring CH stretches Ring stretches 2x Ring stretches (EMIM + ) m (BF 4 ¯) n

Predissociation Yield Photon Energy (cm -1 ) (2,1) (1,2) (1,0) (EMIM + ) m (Cl¯) n

Photon Energy (cm -1 ) Predissociation Yield δ C(2)D δ C(2)H ν C(2)D (2,1) (1,2) (1,0) x5 (EMIM + ) m (Cl¯) n Deuterated

Predissociation Yield Photon Energy (cm -1 ) H-Bonding (EMIM) (EMIM + ) (BF 4 ¯) 2 (EMIM + ) (Cl¯) 2 (EMIM) (Tf 2 N¯) Hydrogen Bonding