NEW METAL-ORGANIC POLYMERIC MATERIALS: FROM DESIGN TO SYNTESIS, STRUCTURAL CHARACTERIZATION AND PROPERTIES.

The modular engineering of heterometallic nanoporous metal-organic frameworks (MOFs) based on novel bis-, tris- and tetra-chelate metalloligands, prepared using the functionalised b-diketones 1,3-bis(4’-cyanophenyl)-1,3-propanedione (HL1), 1,3-bis(4'-pyridyl)-1,3-propanedione (HL2), 1,3-bis(3’- pyridyl)-1,3-propandione (HL3) and 1-(4’-cyanophenyl), 3-phenil-1,3-propandionato (HL4) is described. The square planar complexes [Cu(II)(L)2] (L=L1, L2, L3, L4), the octahedral complxes [M(III)(L)3] (L=L1 and M=Fe3+, Co3+, Al3+, In3+; L=L2 and M=Fe3+, Al3+), [M(II)(L)3](NEt4) (M=Mn2+, Co2+, Zn2+, Cd2+) and the square antiprism/triangular dodecahedron complexes (M(III)(L)4) (L=L1 and M=Tb3+, Eu3+, Nd3+, La3+; L=L2 and M=Nd3+, Eu3+; L=L3 and M =Tb3+, Eu3+, La3+), have been synthesised and characterised. We have prepared different MOFs by reacting the various metalloligands: - the families [M(III)(L1)3Ag3]- X3•Solv and [M(II)(L1)3Ag3]X2•Solv by the reaction of [M(III)(L1)3] and [M(II)(L1)3]- with many silver salts AgX (X=NO3-, BF4-, PF6-, AsF6-, SbF6-, CF3SO3-, tosylate), specifically Very interestingly, all of these network species exhibit the same type of 3D structure and crystallise in the same trigonal space group with similar cell parameters, in spite of the different metal ions, ionic charges and X- counteranions of the silver salts. Anions excahnge experiments have been performed; - a series of MOFs depending on the counter anions used, obtained by [M(III)(L2)3 and different silver salts AgX (X=ClO4-, BF4-, PF6-, AsF6-, SbF6-, CF3SO3-, NO3-, tosylate); - the family [M(III)(L2)M’](X)n obtained reacting [M(III)(L2)3] with CdCl2, CdSO4, MnBr2, CuBF4. These 3D species are chiral and have a entangled system of channels (~60% of unit cell). They crystallise in the same cubic space group and are isostructural, even if we used different metal ions (inside and outer the ML) and counter-anions in the sysnthesis; - a series of lanthanide MOFs by the reaction of [M(III)(L1)4] with silver salts. The syntheis of these polymers depends by the ML:Ag ratio and the system solvent used. The photophysic properties have been studied; - an high porous 3D (70% of the unit cell is free void) species [Cu(L2)(H2O)2]Cl. All these polymer have been structurally characterized by single crystal X-ray analysis.