Smart Grafting of Lanthanides onto Silica via <i>N</i>,<i>N</i>‑Dialkylcarbamato Complexes
Lidia Armelao
Daniela Belli Dell’Amico
Luca Bellucci
Gregorio Bottaro
Luca Labella
Fabio Marchetti
Simona Samaritani
10.1021/acs.inorgchem.5b02535.s002
https://acs.figshare.com/articles/journal_contribution/Smart_Grafting_of_Lanthanides_onto_Silica_via_i_N_i_i_N_i_Dialkylcarbamato_Complexes/2086705
The
grafting and the postgrafting functionalization of lanthanide ions
on commercial amorphous silica have been herein carried out by using
as a precursor the terbium <i>N</i>,<i>N</i>-dibutylcarbamato
derivative [Tb(O<sub>2</sub>CNBu<sub>2</sub>)<sub>3</sub>]. The reaction
of the complex with the surface silanols involved only a fraction
of the carbamato ligands. The following protolytic substitution of
the residual carbamato ligands was carried out by exploiting the Brønsted’s
acidity of the β-diketone dibenzoylmethane (Hdbm), in view of
the antenna effect of the β-diketonato groups, which are commonly
used in lanthanide photoluminescence studies. The reaction proceeded
at room temperature in a clean and easy way affording the introduction
of the chosen functionality in the lanthanide coordination sphere.
The same procedure has been followed by using as a precursor the X-ray
characterized heterometallic <i>N</i>,<i>N</i>-dibutylcarbamato complex [NH<sub>2</sub>Bu<sub>2</sub>]<sub>2</sub>[Ln<sub>4</sub>(CO<sub>3</sub>)(O<sub>2</sub>CNBu<sub>2</sub>)<sub>12</sub>] (Ln = Eu, Tb, Tm). In both cases, X-ray photoelectron
spectroscopy evidenced the chemical implantation of the lanthanide
ions on the silica surface, and photoluminescence studies pointed
out the potentiality of the proposed synthetic approach in the preparation
of highly luminescent materials.
2016-01-19 00:00:00
Br ønsted acidity
carbamato ligands
lanthanide ions
precursor
NH
lanthanide photoluminescence studies
surface
Tb
lanthanide coordination sphere