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Nanoindentation as a probe for mechanically-induced molecular migration in layered organic donor-acceptor complexes

Varughese, S and Kiran, MSRN and Ramamurty, U and Desiraju, GR (2012) Nanoindentation as a probe for mechanically-induced molecular migration in layered organic donor-acceptor complexes. In: Chemistry - An Asian Journal, 7 (9). pp. 2118-2125.

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Official URL: http://dx.doi.org/10.1002/asia.201200224

Abstract

Nanoindentation and scratch experiments on 1:1 donor-acceptor complexes, 1 and 2, of 1,2,4,5-tetracyanobenzene with pyrene and phenanthrene, respectively, reveal long-range molecular layer gliding and large interaction anisotropy. Due to the layered arrangements in these crystals, these experiments that apply stress in particular directions result in the breaking of interlayer interactions, thus allowing molecular sheets to glide over one another with ease. Complex 1 has a layered crystal packing wherein the layers are 68° skew under the (002) face and the interlayer space is stabilized by van der Waals interactions. Upon indenting this surface with a Berkovich tip, pile-up of material was observed on just one side of the indenter due to the close angular alignment of the layers with the half angle of the indenter tip (65.35°). The interfacial differences in the elastic modulus (21 ) and hardness (16 ) demonstrate the anisotropic nature of crystal packing. In 2, the molecular stacks are arranged in a staggered manner; there is no layer arrangement, and the interlayer stabilization involves C-H�N hydrogen bonds and ��� interactions. This results in a higher modulus (20 ) for (020) as compared to (001), although the anisotropy in hardness is minimal (4 ). The anisotropy within a face was analyzed using AFM image scans and the coefficient of friction of four orthogonal nanoscratches on the cleavage planes of 1 and 2. A higher friction coefficient was obtained for 2 as compared to 1 even in the cleavage direction due to the presence of hydrogen bonds in the interlayer region making the tip movement more hindered. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Item Type: Journal Article
Additional Information:
Keywords: charge-transfer complexes; layered compounds; mechanical anisotropy; molecular migration; nanoindentatio
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Division of Mechanical Sciences > Materials Engineering (formerly Metallurgy)
Date Deposited: 17 Sep 2012 11:48
Last Modified: 17 Sep 2012 11:48
URI: http://eprints.iisc.ernet.in/id/eprint/45037

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