We present a proof-of-principle study of an environmentally-friendly approach to laboratory research, in which the synthesis and structural characterisation of metal–organic complexes and frameworks are achieved without using bulk solvents; our study addresses the use of heteroditopic ligands for manipulating the dimensionality of metal–organic materials and describes how kinetic obstacles in such mechanosynthesis can be overcome.
Mechanochemical methods of neat grinding and liquid-assisted grinding have been applied for the synthesis of mono- and bis-thioureas using the click coupling of aromatic and aliphatic diamines with aromatic isothiocyanates. The ability to modify the reaction conditions allowed the optimization of each reaction, leading to the quantitative formation of chiral bis-thioureas with known uses as organocatalysts or anion sensors.
The mechanochemical click coupling of isocyanates and amines has been used as a model reaction to demonstrate that the concept of a solvent-free research laboratory, in which the use of bulk solvents for either chemical synthesis or structural characterization, is applicable to the synthesis of small organic molecules. Whereas the click coupling is achieved in high yields by simple manual grinding of reactants, the use of an electrical, digitally controllable laboratory mill provides a rapid, quantitative and general route to symmetrical and non-symmetrical aromatic or aromatic-aliphatic thioureas. The enhanced efficiency of electrical ball milling techniques, such as neat grinding or liquid-assisted grinding, over manual mortar-and-pestle synthesis is demonstrated throughout the synthesis of 49 different thiourea derivatives. Comparison of powder X-ray diffraction data of mechanochemical products with structural information found in the Cambridge Structural Database (CSD), or obtained herein through single crystal X-ray diffraction, indicates that the mechanochemically obtained thiourea derivatives are pure in chemical sense, but can also demonstrate purity in a supramolecular sense, i.e. in all structurally explored cases the product consisted of a single polymorph. As an extension of our previous work on solvent-free synthesis of coordination polymers, it is now demonstrated that such polymorphic and chemical purity of selected thiourea derivatives, the latter being evidenced through quantitative reaction yields, can enable the immediate solvent-free structural characterization through powder X-ray diffraction aided by solid-state NMR spectroscopy.
This review briefly discusses recent advances and future prospects in the mechanochemical synthesis of coordination compounds by ball milling and grinding, and highlights our contributions to the mechanosynthesis of porous metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs), metal-organic pharmaceutical derivatives and metallodrugs using the recently developed mechanochemical methods of liquid-assisted grinding (LAG) and ion- and liquid-assisted grinding (ILAG).
Oral presentation: |
Vjekoslav Štrukil, László Fábián, David G. Reid, Melinda J. Duer, Graham J. Jackson, Mirjana Eckert-Maksić i Tomislav Friščić: Towards an environmentally-friendly research laboratory - a curious case of metal-organic mechanosynthesis
XXII Croatian meeting of chemists and chemical engineers 13.-16. 02. 2011. Zagreb, Croatia |
Oral presentation: |
Tomislav Friščić: "Mechanochemical synthesis: an overlooked path to clean and efficient synthesis of materials and molecules"
Spring 2011 National ACS Meeting, 11. 03. 2011. Anaheim, California, USA |
Invited lecture: |
Tomislav Friščić: "Energy- and solvent-efficient synthesis of materials and molecules using solid-state transformations"
Max-Planck Society Symposium, 11. 03. 2011. Duesseldorf, Grermany |
Invited lecture: |
Tomislav Friščić: "How to be efficient and environmentally-friendly at the same time: solid-state routes to materials and molecules"
20th Croatian-Slovenian Crystalographic Meeting, June 15-19, 2011.,Baška, Croatia |
Poster presentation: |
Vjekoslav Štrukil, László Fábián, David G. Reid, Melinda J. Duer, Graham J. Jackson, Mirjana Eckert-Maksić i Tomislav Friščić: "Mechanochemical Synthesis of Zinc and Cadmium Metal-Organic Frameworks – The Story of Dimensionality and Solid-State Reactivity"
XX International Conference on the Chemistry of the Organic Solid State, 26. – 30. lipnja 2011., Bangalore, Indija |
Poster presentation: |
Vjekoslav Štrukil, Marina Diana Igrc, Tomislav Friščić i Mirjana Eckert-Maksić: "A Green Route Towards Sustainable Organic Synthesis - Exploiting the Power of Mechanochemistry"
17th European Symposium on Organic Chemistry, 10.-15. srpnja 2011., Hersonissos, Creta, Grčka |
Poster presentation: |
Vjekoslav Štrukil, Marina Diana Igrc, László Fábián, Mirjana Eckert-Maksić i Tomislav Friščić: "Organic Chemistry Without Bulk Organic Solvent - Mechanochemical Opportunities for an Environmentally-Friendly Research"
The 2nd Symposium on Mechanochemistry and Solvent-free Synthesis, 17.-19. kolovoza 2011., Queen's University of Belfast, Belfast, UK |
Oral presentation |
Tomislav Friščić: "Clean, rapid and energy-efficient synthesis of materials and molecules through mechanochemical transformations"
European Congres and Exhibition on Advanced Materials and Processes, September 2011., Montpellier, France. |
Invited lecture |
Tomislav Friščić: "Supramolecular concepts in mechanochemical synthesis"
Joint Midwest/Great Lakes Regional ACS Meeting, St. Louis, USA, October, 2011 |
Oral and poster presentation |
Davor Margetić, Vjekoslav Štrukil, Marina Diana Igrc, László Fábián, Mirjana Eckert-Maksić i Tomislav Friščić: "Environmentally-friendly organic chemistry without bulk organic solvent: mechanochemical synthesis of thioureas"
International Symposium on catalysis and Fine Chemicals 2011 (C&FC2011), Nara, Japan, December 4-8, 2011 |
Poster presentation |
Vjekoslav Štrukil, László Fábián, D. G. Reid, M.J. Duer, J. Jackson, Mirjana Eckert-Maksić, Tomislav Friščić i Davor Margetić: "Mechanochemical synthesis of guanidine metal-organic materials"
International Symposium on Nano Science and Functional Materials, a Post-symposium of International Symposium on catalysis and Fine Chemicals 2011 (C&FC2011), Tokyo Metropolitan University, Tokyo, Japan, December 10, 2011. |
Oral presentation |
Davor Margetić, Vjekoslav Štrukil, Marina Diana Igrc, László Fábián, Mirjana Eckert-Maksić i Tomislav Friščić: "Environmentally-friendly organic chemistry without bulk organic solvent: mechanochemical synthesis of thioureas"
International Symposium on Surface Science (ISSS-6), Funabori, Tokyo, Japan, December 11-15, 2011. |
Poster presentation |
Davor Margetić, Mirjana Eckert-Maksić, Vjekoslav Štrukil: "Density functional study of cimetidine complexation with metals"
Conference on Coordination Chemistry, Organometallic Chemistry and Catalysis, Metabief, France, June 3-8, 2012. |
Poster presentation |
M. Eckert-Maksić: "Solvent-free quantitative synthesis of thiourea organocatalysts and anion sensors by click-mechanochemistry"
Conference on Coordination Chemistry, Organometallic Chemistry and Catalysis, Metabief, France, June 3-8, 2012 |
Poster presentation |
V. Štrukil, L. Fábián, D. G. Reid, M. J. Duer, G. J. Jackson, M. Eckert-Maksić, T. Friščić and D. Margetić: "Mechanochemical synthesis of guanidine - Zinc and Cadmium metal-organic frameworks"
Challenges in Organic Chemistry and Chemical Biology, Edinburgh, UK, June 12-15, 2012. |
Poster presentation |
M. Eckert-Maksić: "Solvent-free quantitative synthesis of thiourea organocatalysts and anion sensors by click-mechanochemistry"
Challenges in Organic Chemistry and Chemical Biology, Edinburgh, UK, June 12-15, 2012 |
Invited lecture:
Tomislav Friščić: "Clean synthesis of materials and molecules through mechanochemical transformations"
Max-Planck Institute for Solid State Research, 11. 02. 2011. Stuttgart, Grermany |
Invited lecture:
Mirjana Eckert-Maksić: "Solvent-free quantitative synthesis of thiourea organocatalysts and anion sensors by click-mechanochemistry"
University of Rome, March 19-24, 2011. Rome, Italy |
Seminar:
Vjekoslav Štrukil: "Dostignuća u mehanokemijskoj sintezi - Ekološki odjeci kemije 21. stoljeća"
Seminar of Department of Organic and Bioorganic Chemistry and Section for Organic Chemistry of Croatian Chemical Society
Ruđer Bošković Institute, 06. 06. 2011. Zagreb, Croatia |
Invited lecture:
Tomislav Friščić: "How to be efficient and environmentally-friendly at the same time: solid-state chemistry of materials and molecules"
Marianopolis College CEGEP, Montreal Canada, October, 2011 |
Invited lecture:
Tomislav Friščić: "Mechanochemistry: developing rapid and general routes for the green and low-energy synthesis of molecules and materials"
Concordia University, Montreal, Canada, October, 2011 |
Invited lecture:
Mirjana Eckert-Maksić: "Guanidines from theory and synthesis to applications"
Institute of Organic and Bioorganic Chemistry, October 11, 2011., Prague, Czech Republic |
Invited lecture:
Margetić, D.; Štrukil, V.; Eckert-Maksić, M.; Igrc, M. D.; Friščić, T.; Fábián, L.; Reid, D. G.; Duer, M. J.; Jackson, J.: "Mechanochemistry - environmentally friendly method for modification and synthesis of pharmaceuticals"
Faculty of pharmaceutical sciences, Musashino university, Tokyo, Japan, December 20, 2011. |
Lecture for students from Graduate School of Mathematics, Computational Sciences and Angineering Sciences, University of Strasbourg:
Vjekoslav Štrukil: "Green Synthetic Methods in Organic Chemistry"
Ruđer Bošković Institute, 27. 03. 2012. Zagreb, Croatia |
