ePrints@IIScePrints@IISc Home | About | Browse | Latest Additions | Advanced Search | Contact | Help

Conformation-Changing Aggregation in Hydroxyacetone: A Combined Low-Temperature FTIR, Jet, and Crystallographic Study

Sharma, Archna and Reva, Igor and Fausto, Rui and Hesse, Susanne and Xue, Zhifeng and Suhm, Martin A and Nayak, Susanta K and Sathishkumar, Ranganthan and Pal, Rumpa and Row, Tayur Guru N (2011) Conformation-Changing Aggregation in Hydroxyacetone: A Combined Low-Temperature FTIR, Jet, and Crystallographic Study. In: Journal of the American Chemical Society, 133 (50). pp. 20194-20207.

[img] PDF
Conformation.pdf - Published Version
Restricted to Registered users only

Download (5MB) | Request a copy
[img] PDF
Supporting_onfo.pdf - Published Supplemental Material
Restricted to Registered users only

Download (138kB) | Request a copy
[img] Plain Text
cg201003d_si_001.cif - Published Version
Restricted to Registered users only

Download (35kB) | Request a copy
Official URL: http://pubs.acs.org/doi/abs/10.1021/ja2030646

Abstract

Aggregation in hydroxyacetone (HA) is studied using low-temperature FTIR, supersonic jet expansion, and X-ray crystallographic (in situ cryocrystallization) techniques. Along with quantum chemical methods (MP2 and DFT), the experiments unravel the conformational preferences of HA upon aggregation to dinners and oligomers. The O-H center dot center dot center dot O=C intramolecular hydrogen bond present in the gas-phase monomer partially opens upon aggregation in supersonic expansions, giving rise to intermolecular cooperatively enhanced O-H center dot center dot center dot O-H hydrogen bonds in competition with isolated O-H center dot center dot center dot O=C hydrogen bonds. On the other hand, low-temperature IR studies on the neat solid and X-ray crystallographic data reveal that HA undergoes profound conformational changes upon crystallization, with the HOCC dihedral angle changing from similar to 0 degrees in the gas phase to similar to 180 degrees in the crystalline phase, hence giving rise to a completely new conformation. These conclusions are supported by theoretical calculations performed on the geometry derived from the crystalline phase.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to American Chemical Society.
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Depositing User: Id for Latest eprints
Date Deposited: 15 Feb 2012 09:36
Last Modified: 15 Feb 2012 09:37
URI: http://eprints.iisc.ac.in/id/eprint/43443

Actions (login required)

View Item View Item