Trimorphic paracetamol, one of the most commonly used analgesic and antipyretic drugs, has been a model system for studying transformations among phases of molecular crystalline materials. During crystallization from the melt and the glass above 0 °C, three new polymorphs of paracetamol (N-acetyl-para-aminophenol or acetaminophen) were discovered, doubling the number of known ambient forms. The crystal structure of one new form was solved using a combination of powder X-ray diffraction and computational techniques. Growth kinetics became anomalous near the glass transition: as temperature decreased, growth rate increased; this rare and poorly understood phenomenon is commonly identified as the glass-to-crystal (GC) growth mode. In addition, two polymorphs displayed optical evidence of helicoidal morphologies, a characteristic of at least 25% of molecular crystals, that has been resistant to a universal explanation.
Polymorphism of aspirin (acetylsalicylic acid), one of the most widely consumed medications, was equivocal until the structure of a second polymorph II, similar in structure to the original form I, was reported in 2005. Here, the third ambient polymorph of aspirin is described. It was crystallized from the melt, and its structure was determined using a combination of X-ray powder diffraction analysis and crystal structure prediction algorithms.
Single crystal X-ray diffraction is arguably the most definitive method for molecular structure determination, but the inability to grow suitable single crystals can frustrate conventional X-ray diffraction analysis. We report herein an approach to molecular structure determination that relies on a versatile toolkit of guanidinium organosulfonate hydrogen-bonded host frameworks that form crystalline inclusion compounds with target molecules in a single-step crystallization, complementing the crystalline sponge method that relies on diffusion of the target into the cages of a metal-organic framework. The peculiar properties of the host frameworks enable rapid stoichiometric inclusion of a wide range of target molecules with full occupancy, typically without disorder and accompanying solvent, affording well-refined structures. Moreover, anomalous scattering by the framework sulfur atoms enables reliable assignment of absolute configuration of stereogenic centers. An ever-expanding library of organosulfonates provides a toolkit of frameworks for capturing specific target molecules for their structure determination.
Bi-Oxazoline (biOx) has emerged as an effective ligand framework for promoting nickel-catalyzed cross-coupling, cross-electrophile coupling, and photoredox-nickel dual catalytic reactions. This report fills the knowledge gap of the organometallic reactivity of (biOx)Ni complexes, including catalyst reduction, oxidative electrophile activation, radical capture, and reductive elimination. The biOx ligand displays no redox activity in (biOx)Ni(I) complexes, in contrast to other chelating imine and oxazoline ligands. The lack of ligand redox activity results in more negative reduction potentials of (biOx)Ni(II) complexes and accounts for the inability of zinc and manganese to reduce (biOx)Ni(II) species. On the basis of these results, we revise the formerly proposed "sequential reduction" mechanism of a (biOx)Ni-catalyzed cross-electrophile coupling reaction by excluding catalyst reduction steps.
Water-responsive materials undergo reversible shape changes upon varying humidity levels. These mechanically robust, yet flexible structures can exert significant forces and hold promise as efficient actuators for energy harvesting, adaptive materials, and soft robotics. Here we demonstrate that energy transfer during evaporation-induced actuation of nanoporous tripeptide crystals results from strengthening of water H-bonding that drives the contraction of the pores. The seamless integration of mobile and structurally bound water inside these pores with a supramolecular network which contains readily deformable aromatic domains, translates dehydration-induced mechanical stresses through the crystal lattice, suggesting a general mechanism of efficient water-responsive actuation.The observed strengthening of water bonding complements accepted understanding of capillary force induced reversible contraction for this class of materials. These minimalistic peptide crystals are much simpler in composition compared to natural water-responsive materials, and the insights provided here can be applied more generally for the design of high-energy molecular actuators.
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