In this highlight, the reasons for the widespread interest generated by ionic co-crystals, namely those formed by a neutral molecule and a salt, are addressed. In particular, the class of compounds obtained by co-crystallization of neutral organic molecules and inorganic salts (e.g. alkali and alkaline earth halides, sulfates, phosphates etc.) is discussed with the focus on their applications in diverse areas, such as pharmaceuticals, food and fertilizers, and also in chiral resolution. It is argued that, in terms of structure and intermolecular bonding features, these compounds do not differ from classical coordination compounds (complexes) and that their popularity arises from the effectiveness of the organic–inorganic assembly to enhance thermal stability, improve particle size and morphology and change significantly the solubility and dissolution rate with respect to those of the pure active ingredients.

Organic–inorganic ionic co-crystals: a new class of multipurpose compounds

Density functional study of spectroscopy, electronic structure, linear and nonlinear optical properties of l-proline lithium chloride and l-proline lithium bromide monohydrate: For laser applications

Collagen piezoelectricity has been the focus of a large number of experimental and theoretical studies for over fifty years. Less is known about the piezoelectric properties of its building blocks, in particular but not limited to, proline and hydroxyproline. Spurred by the recent upsurge of interest in piezoelectricity in organic crystals including our own report of unprecedentedly high piezoelectricity in amino acid glycine, we predict and measure the piezoelectric properties of collagen subcomponents in single crystalline forms and the collagen-like alanine-hydroxyproline-glycine trimer peptide. We map the modulation of piezoelectric charge constants in collagen building blocks as the crystal symmetry is lowered and the molecule size increases, finding strong evidence for amino acid-level barcoding of collagen piezoelectricity that can in turn be tuned using very simple chemistry. The simple addition of an -OH group can increase piezoelectric constants by up to two orders of magnitude (d25 = 25 ± 5 pC N-1) as measured in Y-cut hydroxyproline crystals. The value is similar to that obtained from thermoelectrically poled commercial polyvinylidene di fluoride (PVDF) films. Overall, our findings support a simple block by block approach in which first principles calculations can guide the understanding and re-engineering of piezoelectric biomolecules.

Deconstructing collagen piezoelectricity using alanine-hydroxyproline-glycine building blocks

The preparation and characterization of a whole family of hydrated ionic co-crystals formed by both enantiopure l-proline and racemic dl-proline with LiX (X=Cl, Br, I) are reported. The chiral preference of the lithium cation for homochiral coordination, both in the formation of crystalline conglomerates (with Cl and Br) and racemates (with Cl and I), in which molecules of opposite chirality are confined to distinct crystal layers, is discussed. Dehydration processes for all hydrated crystals have also been investigated.

Ionic Co-Crystal Formation as a Path Towards Chiral Resolution in the Solid State.

Homochiral cadmium chlorides were prepared under mild conditions using enantiopure amino acids as structure-directing agents. They feature a lacunary hexagonal CdCl2 lattice as well as a one-dimensional perovskite structure. The coexistence of protonated and zwitterionic amino acids between cadmium chloride chains is quite rare. These compounds are nonlinear optically active solids showing a moderate second-harmonic-generation response. Theoretical calculations were performed to reveal the origin of their nonlinear-optical properties.

Homochiral Hybrid Organic-Inorganic Cadmium Chlorides Directed by Enantiopure Amino Acids.

Synthesis, structure, crystal growth and characterization of a novel semiorganic nonlinear optical l-proline lithium bromide monohydrate single crystal.

Laser damage threshold, antimicrobial efficacy and physicochemical properties of an organometallic L-proline lithium chloride monohydrate single crystal for NLO application and optoelectronic device fabrication

Investigation of physicochemical properties, photoluminescence, laser damage threshold, antimicrobial, NLO activity of L-proline manganese chloride monohydrate for optoelectronic applications

Second harmonic generation, photoluminescence and laser damage threshold of L–Proline strontium chloride monohydrate: a prospective NLO tunable band gap for optoelectronic applications

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Papers

Synthesis, structure, crystal growth and characterization of a novel semiorganic nonlinear optical l-proline lithium bromide monohydrate single crystal.

Laser damage threshold, antimicrobial efficacy and physicochemical properties of an organometallic L-proline lithium chloride monohydrate single crystal for NLO application and optoelectronic device fabrication

Investigation of physicochemical properties, photoluminescence, laser damage threshold, antimicrobial, NLO activity of L-proline manganese chloride monohydrate for optoelectronic applications

Investigation of physicochemical properties, photoluminescence, laser damage threshold, antimicrobial, NLO activity of L-proline manganese chloride monohydrate for optoelectronic applications

Second harmonic generation, photoluminescence and laser damage threshold of L–Proline strontium chloride monohydrate: a prospective NLO tunable band gap for optoelectronic applications