Factors Affecting Copper(II) Binding to Multiarmed Cyclam-Grafted Mesoporous Silica in Aqueous Solution

Abstract

Single- as well as multi-anchored cyclam-functionalized silica samples have been prepared by grafting amorphous silica gel (K60) and mesostructured silica (SBA-15) with silylated cyclam precursors bearing one, two, or four triethoxysilyl groups, respectively ascribed to cyclam-mono, cyclam-di, and cyclam-tetra. Their reactivity toward copper(II) has been thoroughly investigated in aqueous solution and discussed with respect to the number of arms tethering the ligand to the silica surface and the structural ordering of the adsorbent in terms of capacity, long-term stability, and speed of access to the binding sites. Less-than-complete metal ion uptake was always observed, even in excess of cyclam groups with respect to solution-phase Cu(II), suggesting lower stability of immobilized complexes relative to those in solution. Therefore, the number of arms attaching cyclam moieties to the silica walls (one, two, or four) was found to dramatically affect the binding properties of these hybrids toward copper(II), revealing significantly larger capacities when reducing the number of arms (less rigidity constraints in the macrocycle). In parallel, multiarm tethering resulted in better chemical resistance toward degradation as evidenced by UV-visible monitoring of Cu-cyclam complexes in solution (i.e., more ligand leaching from the adsorbent for singly tethered cyclam). On the other hand, electron spin resonance (ESR) experiments did not evidence significant differences between complexes bearing one, two, or four alkyl arms, since all Cu(II)-cyclam surface complexes were found to be hexacoordinated with a strong equatorial ligand field. Comparison of amorphous gels and mesostructured materials indicates that the binding properties of the adsorbents were hardly influenced by their level of ordering, suggesting that accessibility to the binding sites was not the limiting factor. Some advantage belonging to mesostructured adsorbents was however observed with respect to the rate of access to the active centers at pH values close to neutrality (due to faster mass transport), but this was no more the case when operating at lower pH values where the formation of the Cu-cyclam complex became the rate-determining step, as pointed out by electrochemistry.