Remarkably Distinct Mechanical Flexibility in Three Structurally Similar Semiconducting Organic Crystals Studied by Nanoindentation and Molecular Dynamics

Abstract

Distinct macroscopic mechanical responses of the three crystals of naphthalene diimide derivatives, 1Me, 1Et, and 1nPr, studied here are very intriguing because their molecular structures are very similar, with the difference only in the alkyl chain length. Among the three crystals examined, 1Me shows highly plastic bending nature, 1Et shows elastic flexibility, and 1nPr is brittle. A detailed investigation by nanoindentation and molecular dynamics (MD) simulations allowed us to correlate their distinct mechanical responses with the way the weak interactions pack in crystal structures. The elastic modulus (E) of 1Me is nearly an order of magnitude lower than that of 1Et, whereas hardness (H) is less than half. The low values of E and H of 1Me indicate that these crystals are highly compliant and offer a low resistance to plastic flow. As the knowledge of hardness and elastic modulus of molecular crystals alone is insufficient to capture their macroscopic mechanical deformation nature, that is, elastic, brittle, or plastic, we have employed three-point bending tests using the nanoindentation technique. This allowed a quantitative evaluation of flexibility of the three mechanically distinct semiconducting molecular crystals, which is important for designing larger-scale applications; these were complemented with detailed MD simulations. The elastic 1Et crystals showed remarkable flexibility even after 1000 cycles. The results emphasize that the alkyl side chains in functional organic crystals may be exploited for tuning their self-assembly as well as their mechanical properties. Hence, the study has broad implications, for example, in crystal engineering of various flexible, ordered molecular materials.

Single Atom Substitution Alters the Polymorphic Transition Mechanism in Organic Electronic Crystals

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Intermolecular Interactions in Functional Crystalline Materials: From Data to Knowledge

“…Vice versa, a corrugated molecular structure of celecoxib without any slip-planes and numerous weak interactions in orthogonal directions were suggested to be the reasons for exceptionally high elasticity of its needle singe crystals [176]. Flat naphthalene diimine derivatives were found to have comparable crystal packing governed by π...π stacking, similar crystal morphology, but exhibited various mechanical flexibility attributed to close packing or interlock of their terminal alkyl chains [177]. Investigation of sulfa drug crystals [178], co-crystals of vanillin isomers [179], and amino acids [180] demonstrated that H-bonded layered structures with orthogonal distribution of strong and weak interactions attain the feasibility of cleaving a crystal along a given crystallographic plane parallel with these robust synthons.Particularly, single crystals with molecular surfaces formed by hydrophobic interactions can be applied as clean surfaces for molecular beam epitaxy.…”

Plastically Bendable Crystals of Flufenamic Acid Form III

“…Quantitative nanoindentation experiments were performed on the (100) face of the straight crystal to explore the accurate mechanical properties of the bending face. [42][43][44] The representative load (P) versus depth (h) curve is shown in Fig. 1d.…”