Development of New Methodologies for Inorganic Synthesis

Traditional chemical wisdom often cites Aristotle ‘compounds do not react unless fluid or dissolved’ as one of the original sources contributing to the default assumption of the need for solvents in molecular syntheses. This dogma of indispensable solvent use for chemical syntheses has existed for many centuries and has often been counterproductively deep-rooted in the minds of molecular synthetic chemists. There are distinct advantages to using solvents, primarily to promote the interaction of reagents, accelerate reaction rates, potentially alter the distribution of products, and the facile separation and purification of products. However, cleaner and more environmentally friendly synthetic technologies have become of pinnacle importance in both academia and industry, since commonly used organic solvents in laboratories and chemical industries are recognized as wasteful and environmentally unsustainable. Among the emergent eco-friendly alternatives is mechanochemistry.

Our work has been instrumental in the expansion of mechanochemistry to molecular main group materials. We have pioneered the area of synthetic main group mechanochemistry and set the foundations for the future design of sustainable synthetic methodologies in the area of main‐group chemistry.

 

Selected publications:

• Direct and Telescopic Mechanochemical Synthesis of Higher-order Organic-Inorganic Hybrid Cocrystals: Tuning Order, Functionality and Size in Cocrystal Design. Z. X. Ng, D. Tan, T. Wei Liang, F. Leon, X.-Y. Shi, Y. Sim, Y. Li, R. Ganguly, Z. Yanli, M. Sharmarke* and F. García*. ChemRxiv 2021, DOI: 10.26434/chemrxiv.13515938.v1.
• Metal Complexes in Mechanochemistry. Felix León and Felipe García*. Reference Module in Chemistry, Molecular Sciences and Chemical Engineering (Comprehensive Coordination Chemistry III), 2021. DOI: 10.1016/B978-0-08-102688-5.00031-3. Invited contribution
• Upscaling Mechanochemistry: Challenges and Opportunities for Sustainable Industry. Evelina Colacino,* Valerio Isoni,* Deborah Crawford,* Felipe Garcia.* Trends in Chemistry, 2021, Accepted DOI: 10.1016/j.trechm.2021.02.00. Invited Science & Society article.
• Multi-gram Mechanosynthesis of Salophen-Complex: A Comparative Analysis. V. K. Singh, A. Chamberlain-Clay, H. C. Ong, F. León, G. Hum, M. Y. Par, P. Daley-Dee, F. García.* ACS Sust. Chem. & Eng., 2021, Accepted DOI: 10.1021/acssuschemeng.0c06374.
• Completely Solvent-free Protocols to Access Phase-Pure, Metastable Metal Halide Perovskites and Functional Photodetectors from the Precursor Salts. iScience, 2019, Accepted. DOI: 10.1016/j.isci.2019.05.042
  
• Main Group  Mechanochemistry: From Curiosity to Established Protocols.  Chem. Soc. Rev., 2019, 48, 2274-2292. DOI: 10.1039/C7CS00813A.
• Orthogonality in Main Group Compounds: Direct One-step Synthesis of Air- and Moisture-stable Cyclophosphazanes by Mechanochemistry.  ChemComm., 2018, DOI: 10.1039/C8CC01043A . (Invited contribution to Emerging Investigators 2018)
• Main Group Mechanochemistry. Beilstein J. Org. Chem. 2017, 13, 2068-2077. DOI: 10.3762/bjoc.13.204 (Invited contribution to a Thematic series: “Mechanochemistry”).
• Mechanochemical Synthesis of Phosphazane-Based Compounds.   Chem. Eur. J. , 2017, 23, 11279–11285. DOI:10.1002/chem20171619. (Selected as Hot Paper)
• Multi-Step Solvent-Free Mechanochemical Route to Indium(III) Complexes .  Dalton Trans., 2016, 45, 7941 – 7946. DOI: 10.1039/C6DT00978F
  
• Mechanochemistry Made It Possible: Synthesis of the Sterically Encumbered Phosphazane P₄(N^tBu)₆.  Angew. Chem. Int. Ed., 2016, 55,12736 – 12740. DOI: 10.1002/anie.201605936. (Selected as Hot Paper)