We present the one-dimensional optical-waveguiding crystal dithieno[3,2-a:2',3'-c]phenazine with a high aspect ratio, high mechanical flexibility, and selective self-absorbance of the blue part of its fluorescence (FL). While macrocrystals exhibit elasticity, microcrystals deposited at a glass surface behave more like plastic crystals due to significant surface adherence, making them suitable for constructing photonic circuits via micromechanical operation with an atomic-force-microscopy cantilever tip. The flexible crystalline waveguides display optical-path-dependent FL signals at the output termini in both straight and bent configurations, making them appropriate for wavelength-division multiplexing technologies. A reconfigurable 2×2-directional coupler fabricated via micromanipulation by combining two arc-shaped crystals splits the optical signal via evanescent coupling and delivers the signals at two output terminals with different splitting ratios. The presented mechanical micromanipulation technique could also be effectively extended to other flexible crystals.

Mechanophotonics: Flexible Single-Crystal Organic Waveguides and Circuits.

Next-Generation Organic Photonics: The Emergence of Flexible Crystal Optical Waveguides

The discovery of molecular single crystals that display interesting elastic behaviour has generated excitement regarding their potential applications as it has upended the common perception of crystals as brittle objects. In order to design new functional materials based on molecular crystals, a comprehensive understanding of how these materials respond to deformation on a molecular-level is required. An introduction to the underlying mechanical theory and how it may be applied to single crystals is provided, along with a comprehensive discussion on how these mechanical properties can be characterised. While this field has already presented a large number of elastically flexible crystals, there is a lack of detailed mechanical characterisation data and some contention regarding the atomic-scale mechanism of elasticity. Due to the discrepancies and contradictions between theories proposed in the literature, it is not yet understood why some crystals are elastic while others shatter under applied force. To dispel ambiguity and guide future research, a set of criteria are proposed to define an elastically flexible crystal, so that these materials may find applications among future technologies.

Elastically flexible molecular crystals.

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, br...

/pdf/remarkably-distinct-mechanical-flexibility-in-three-3tegq1w20b.pdf

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

Mechanically Reconfigurable Organic Photonic Integrated Circuits Made from Two Electronically Different Flexible Microcrystals

Crystalline coordination polymers tend to be brittle and inelastic, however, we now describe a family of such compounds that are capable of displaying mechanical elasticity in response to external pressure. The design approach successfully targets structural features that are critical for producing the desired mechanical output. The elastic crystals all comprise 1D cadmium(II) halide polymeric chains with adjacent metal centres bridged by two halide ions resulting in the required stacking interactions and short "4 A" crystallographic axes. These polymeric chains (structural "spines") are further organized via hydrogen bonds and halogen bonds perpendicular to the direction of the chains. By carefully altering the strength and the geometry of these non-covalent interactions, we have demonstrated that it is possible to control the extent of elastic bending in crystalline coordination compounds.

Mechanically Responsive Crystalline Coordination Polymers with Controllable Elasticity

The mechanical adaptability of a family of six one-dimensional crystalline coordination polymers (CPs) of cadmium ([CdX2(3-X′py)2]n; 1: X = Br, X′ = Cl, 2: X = I, X′ = Cl, 3: X = I, X′ = Br, 4: X =...

Elucidating the Origins of a Range of Diverse Flexible Responses in Crystalline Coordination Polymers

The ability of one-dimensional crystalline coordination polymers of cadmium(II), namely [CdCl2(3-Clpy)2]n (1), [CdCl2(3-Brpy)2]n (2), and [CdBr2(3-Brpy)2]n (3) (3-Clpy = 3-chloropyridine; 3-Brpy = 3-bromopyridine), to adapt to mechanical stimuli was examined and differences in elastic responses were observed. Crystals of 1 and 3 showed similar behaviour with substantial elastic responses to external mechanical force followed by slight plasticity close to the breakage point, where these responses were classified as elastic→plastic. On the other hand, crystals of 2 were found to be less adaptable to mechanical stimuli, displaying only a slight elastic response with a typical brittle breakage. Crystals were further examined by atomic force microscopy while structural features were explored by theoretical methods. The rationalization of the observed mechanical properties in the context of interaction energies and Young's moduli revealed that the stronger interactions are reflected in the larger Young's modulus values, which in turn made the crystals stiffer and consequently less adaptable to external mechanical stimuli.

Exploring the diversity of elastic responses of crystalline cadmium(II) coordination polymers: from elastic towards plastic and brittle responses

Thermally-Induced Reactions of Aromatic Crystalline Nitroso Compounds

The approach for enhancing the elasticity of crystals with suboptimal elastic performances through a rational design was presented. A hydrogen-bonding link was identified as a critical feature in the structure of the parent material, the Cd(II) coordination polymer [CdI2(I-pz)2]n (I-pz = iodopyrazine), to determine the mechanical output and was modified via cocrystallization. Small organic coformers resembling the initial organic ligand but with readily available hydrogens were selected to improve the identified link, and the extent of strengthening the critical link was in an excellent correlation with the delivered enhancement of elastic flexibility materials.

Tailoring Enhanced Elasticity of Crystalline Coordination Polymers

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