The past decade has seen a reawakening of solid-state approaches to chemical synthesis, driven by the search for new, cleaner synthetic methodologies. Mechanochemistry, i.e., chemical transformations initiated or sustained by mechanical force, has been advancing particularly rapidly, from a laboratory curiosity to a widely applicable technique that not only enables a cleaner route to chemical transformations but offers completely new opportunities in making and screening for molecules and materials. This Outlook provides a brief overview of the recent achievements and opportunities created by mechanochemistry, including access to materials, molecular targets, and synthetic strategies that are hard or even impossible to access by conventional means.

http://pubs.acs.org/doi/pdf/10.1021/acscentsci.6b00277

Mechanochemistry: A Force of Synthesis

Mechanochemistry is becoming more widespread as a technique for molecular synthesis with new mechanochemical reactions being discovered at increasing frequency. Whilst mechanochemical methods are solvent free and can therefore lead to improved sustainability metrics, it is more likely that the significant differences between reaction outcomes, reaction selectivities and reduced reaction times will make it a technique of interest to synthetic chemists. Herein, we provide an overview of mechanochemistry reaction examples, with ‘direct’ comparators to solvent based reactions, which collectively seemingly show that solid state grinding can lead to reduced reaction times, different reaction outcomes in product selectivity and in some instances different reaction products, including products not accessible in solution.

/pdf/mechanochemistry-as-an-emerging-tool-for-molecular-synthesis-1fikz7tsl4.pdf

Mechanochemistry as an emerging tool for molecular synthesis: what can it offer?

Mechanochemistry of inorganic solids is a well-established field. In the last decade mechanical treatment has become increasingly popular as a method for achieving selective and “greener” syntheses also in organic systems. New groups and researchers enter the field of mechanochemistry, often re-discovering many of the previously known facts and effects, while at the same time neglecting other important concepts. The author of this contribution has long been involved in mechanochemical research in both inorganic and organic systems. The aim of this contribution is to provide an overview of the basic concepts of mechanochemistry in relation to inorganic and organic systems.

Mechanochemistry of inorganic and organic systems: what is similar, what is different?

Foreword Acknowledgements Definitions of symbols used 1. Some fundamentals 2. The harmonic approximation and lattice dynamics of very simple systems 3. Dynamics of diatomic crystals: general principles 4. How far do the atoms move? 5. Lattice dynamics and thermodynamics 6. Formal description 7. Acoustic modes and macroscopic elasticity 8. Anharmonic effects and phase transitions 9. Neutron scattering 10. Infrared and Raman spectroscopy 11. Formal quantum mechanical description of lattice vibrations 12. Molecular dynamics simulations Appendices Problems Bibliography Index.

Introduction to Lattice Dynamics

Theory of complex spectra.

Organic single crystals that combine mechanical flexibility and optical properties are important for developing flexible optical devices, but examples of such crystals remain scarce. Both mechanical flexibility and optical activity depend on the underlying crystal packing and the nature of the intermolecular interactions present in the solid state. Hence, both properties can be expected to be tunable by small chemical modifications to the organic molecule. By incorporating a chlorine atom, a reportedly mechanically flexible crystal of (E)-1-(4-bromo-phenyl)iminomethyl-2-hydroxyl-naphthalene (BPIN) produces (E)-1-(4-bromo-2-chloro-phenyl)iminomethyl-2-hydroxyl-naphthalene (BCPIN). BCPIN crystals show elastic bending similar to BPIN upon mechanical stress, but exhibit a remarkable difference in their optical properties as a result of the chemical modification to the backbone of the organic molecule. This work thus demonstrates that the optical properties and mechanical flexibility of molecular materials can, in principle, be tuned independently.

Elastic Flexibility in an Optically Active Naphthalidenimine-Based Single Crystal

This chapter provides a brief introduction to the theoretical and experimental techniques used throughout the thesis. Discussion includes an introduction to Density Functional Theory and its practical considerations, an overview of inelastic neutron scattering spectroscopy, X-ray diffraction, and fall hammer explosives testing.

Experimental and Computational Methods

Fluorescent plastically bendable crystals are a promising alternative to silicon‐based materials for fabricating photonic integrated circuits, owing to their optical attributes and mechanical compliance. Mechanically bendable plastic organic crystals are rare. Their formation requires anisotropic intermolecular interactions and slip planes in the crystal lattice. This work presents three fluorescent plastically bendable crystalline materials namely, 2‐((E)‐(6‐methylpyridin‐2‐ylimino)methyl)‐4‐chlorophenol (SB1), 2‐((E)‐(6‐methylpyridin‐2‐ylimino)methyl)‐4‐bromophenol (SB2), and 2‐((E)‐(6‐Bromopyridin‐2‐ylimino)methyl)‐4‐bromophenol (SB3) molecules. The crystal plasticity in response to mechanical stress facilitates the fabrication of various monolithic and hybrid (with a tip‐to‐tip coupling) photonic circuits using mechanical micromanipulation with an atomic force microscope cantilever tip. These plastically bendable crystals act as active (self‐guiding of fluorescence) and passive waveguides both in straight and extremely bent (U‐, J‐, and O‐shaped) geometries. These microcircuits use active and passive waveguiding principles and reabsorbance and energy‐transfer mechanisms for their operation, allowing input‐selective and direction‐specific signal transduction.

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/adom.202201518

Plastically Bendable Organic Crystals for Monolithic and Hybrid Micro‐Optical Circuits

X-ray absorption spectroscopy (XAS) provides a unique, atom-specific tool to probe the electronic structure of solids. By surmounting long-held limitations of powder-based XAS using a dynamically averaged powder in a Resonant Acoustic Mixer (RAM), we demonstrate how time-resolved in situ (TRIS) XAS provides unprecedented detail of mechanochemical synthesis. The use of a custom-designed dispersive XAS (DXAS) setup allows us to increase the time resolution over existing fluorescence measurements from ∼15 min to 2 s for a complete absorption spectrum. Hence, we here establish TRIS-XAS as a viable method for studying mechanochemical reactions and sampling reaction kinetics. The generality of our approach is demonstrated through RAM-induced (i) bottom-up Au nanoparticle mechanosynthesis and (ii) the synthesis of a prototypical metal organic framework, ZIF-8. Moreover, we demonstrate that our approach also works with the addition of a stainless steel milling ball, opening the door to using TRIS-DXAS for following conventional ball milling reactions. We expect that our TRIS-DXAS approach will become an essential part of the mechanochemical tool box.

Dispersive x-ray absorption spectroscopy for time-resolved in situ monitoring of mechanochemical reactions.

Dynamic mechanical stress leads to rapid and transient vibrational excitation of crystalline solids, greatly altering their chemical reactivity. 

Adam A. L. Michalchuk

Papers

Elastic Flexibility in an Optically Active Naphthalidenimine-Based Single Crystal

Experimental and Computational Methods

Plastically Bendable Organic Crystals for Monolithic and Hybrid Micro‐Optical Circuits

Dispersive x-ray absorption spectroscopy for time-resolved in situ monitoring of mechanochemical reactions.

The mechanochemical excitation of crystalline LiN<sub>3</sub>