Polyfunctional Tetraaza-Macrocyclic Ligands: Zn(II), Cu(II) Binding and Formation of Hybrid Materials with Multiwalled Carbon Nanotubes

The binding properties of HL1, HL2, and HL3 ligands toward Cu(II) and Zn( II) ions, constituted by tetraazamacrocyclic rings decorated with pyrimidine pendants, were investigated by means of potentiometric and UV spectrophotometric measurements in aqueous solution, with the objective of using the related HL-M(II) (HL = HL1-HL3; M = Cu, Zn) complexes for the preparation of hybrid MWCNT-HL-M(II) materials based on multiwalled carbon nanotubes (MWCNTs), through an environmentally friendly noncovalent procedure. As shown by the crystal structure of [Cu( HL1)](ClO4)(2), metal coordination takes place in the macrocyclic ring, whereas the pyrimidine residue remains available for attachment onto the surface of the MWCNTs via pi-pi stacking interactions. On the basis of equilibrium data showing the formation of highly stable Cu(II) complexes, the MWCNT-HL1-Cu(II) material was prepared and characterized. This compound proved very stable toward lixiviation processes (release of HL1 and/or Cu(II)); thus, it was used for the preparation of its reduced MWCNT-HL1Cu(0) derivatives. X-ray photoelectron spectroscopy and transmission electron microscopy images showed that MWCNT-HL1Cu(0) contains Cu(0) nanoparticles, of very small (less than 5 nm) and regular size, uniformly distributed over the surface of the MWCNTs. Also, the MWCNT-HL1-Cu(0) material proved very resistant to detachment of its components. Accordingly, both MWCNT-HL1-Cu(II) and MWCNT-HL1-Cu(0) are promising candidates for applications in heterogeneous catalysis.