ABOUT MOFs AND CPs - How and why this field has been developed

1. NACC-1Binuclear entities and metal-organic-frameworks (MOFs): The continuum MOFs/CPs and cocrystals/CPs (coordination polymers)« ON A FUNDAMENTAL LEVEL, MOFs COMBINE CHEMISTRY AND GEOMETRY TO PRODUCE TECHNOLOGY-GENERATING PROPERTIES IN A WAY THAT IS RARELY EXPERIENCED IN SCIENCE » J. R. Long, O. M. Yaghi, Chem. Soc. Rev., 38(5), 1213-1214, (2009)

2. ABOUT MOFs AND CPs - How and why this field has been developed - Why definitions are not straightforward - FROM SALTS OF CARBONATO COMPLEXES TO EXTENDED DICARBOXYLATE FRAMEWORKS - The binuclear copper (II) acetate - Replacing by - FROM CONTINUUM MOFs/CPs to CONTINUUM COCRYSTALS/CPs: COFs? - Two isostructural compounds - The COFs - IMPORTANT DEDUCED POINTS

3. HOOC-(CH2)n-COOH

4. Metals

6. PRACTICAL POINT OF VIEW • STRUCTURAL • DIVERSITY • UNUSUAL • ARCHITECTURES

7. -MOCNs, MOMs • COFs (bonds) • ICPs (structural features) • PCPs (properties) • Extended structures • hybride inorgani-organic materials • supramolecular structures MOFs = « SUPRAMOLECULAR SOLIDS THAT CONSIST OF STRONG BONDING PROVIDING ROBUSTNESS, LINKING UNITS THAT ARE AVAILABLE FOR MODIFICATION BY ORGANIC SYNTHESIS, AND A GEOMETRICALLY WELL-DEFINED STRUCTURE » M. D. Allendorf,…., Chem. Soc. Rev., 38(5), 1330-1352, (2009) = « MATERIALS WITH FRAMEWORKS BUILT BY LINKING POLYATOMIC CLUSTERS (SBUs) ENTIRELY BY STRONG COVALENT BONDS, AND THUS NOT INCLUDING COORDINATION POLYMERS, WHICH HAVE SOME GENERALLY WEAKER BONDS, AND LOWER STABILITY » M. O. Keeffe, Chem. Soc. Rev., 38(5), 1215-1217, (2009) = « INFINITE SYSTEMS BUILD UP WITH METAL IONS AND ORGANIC LIGANDS AS MAIN ELEMENTARY UNITS LINKED VIA COORDINATION BONDS AND OTHER WEAK CHEMICAL BONDS. THESE COMPOUNDS ARE ALSO NAMED MOCNs OR MOFs IN THE CASE OF ORDERED STRUCTURES ». C. Janiak, J. Chem. Soc., Dalton Trans, 2781, (2003) CPs

8. Coordination bonds + H bonds • Coordination bonds + other weaker interactons M-M; ….; CH….  • Coordination bonds + covalent bonds + electrostatic interactions between • Charged species (hybrids solids)

10. What about COFs ? What about hybrid solids ?

11. WEAKER INTERACTION STRONGLY INFLUENCE THE FORMATION OF CPs • IN HYDROGEN BONDS THE STRONGEST HAS A QUASI-COVALENT NATURE WEAK TO INTERMEDIATE STRENGTHS

13. Copper formate • Copper succinate • Copper benzoate Copper oxalate Copper succinate

21. HO2(C4H4O4)3(H2O)4

22. Ca(C3H3O4)2

23. Ce((C3H2O4)3(H2O)3.2H2O

24. Yb2(C4H4O4)3(H2O)4

25. La2(C5H6O4)3(H2O)3.2H2O

27. lsp100K

28. lsp298K

29. Lsp 100K

30. lsp298

31. blg2

32. clm2

33. [H0.5OOC-(CH2)n-COOH0.5]- Supramolecular isomers Bringing out breathing effects ?

44. Building of new polymeric materials: • Binuclear units Supramolecular H-bond networks Extended Frameworks • Crystal engineering generated: • applied in pharmaceutical field • Use of supramolecular synthesis for obtaining cocrystals/salts through

45. Cocrystals and salts = crystalline solids containing two or more building blocks Location of the proton transfer between an acid and a base ?

47. COFs = « is by definition devoid of metals and are constructed entirely from strong covalent bonds » L. J. Murray and al….Chem. Soc. Rev., 38; 1294, (2009) - Only C, H, O and B atoms ?

48. [CO3]2- [HOOC-R-CO2]- [O2C-R-CO2]2- • Several kinds of packing • Binuclear units

49. S. Morris and al….Polyhedron (1998)

50. HIGH STRUCTURAL DIMENSIONALITY LOW HYDRATION DEGREE • HYDROTHERMAL SYNTHESIS LOWER VOID SPACE LOWER WATER CONTENT • MILD CONDITIONS ANHYDROUS MOFs ? • SALTS/COCRYSTALS/EXTENDED FRAMEWORK  Definitions and Nomenclature ? DICARBOXYLIC ACIDS DICARBOXYLATES HYDROGEN BONDS COORDINATION BONDS H SUPRAMOLECULAR SYNTHONS SUPRAMOLECULAR EXTENDED FRAMEWORKS INVOLVING CONNECTORS