A Unique LnIII {[3.3.1]GaIII Metallacryptate} Series That Possesses Properties of Slow Magnetic Relaxation and Visible/Near-Infrared Luminescence

Jacob C Lutter; Svetlana V Eliseeva; Jeff W Kampf; Stéphane Petoud; Vincent L Pecoraro

doi:10.1002/chem.201801355

A Unique Ln^III {[3.3.1]Ga^III Metallacryptate} Series That Possesses Properties of Slow Magnetic Relaxation and Visible/Near-Infrared Luminescence

Chemistry. 2018 Jul 25;24(42):10773-10783. doi: 10.1002/chem.201801355. Epub 2018 Jun 27.

Authors

Jacob C Lutter¹, Svetlana V Eliseeva², Jeff W Kampf¹, Stéphane Petoud², Vincent L Pecoraro¹

Affiliations

¹ Department of Chemistry, Willard H. Dow Laboratories, University of Michigan, Ann Arbor, MI, 48109, USA.
² Centre de Biophysique Moléculaire, CNRS UPR 4301, 45071, Orléans Cedex 2, France.

PMID: 29770506
DOI: 10.1002/chem.201801355

Abstract

A new family of [3.3.1] metallacryptates with the general composition [LnGa₆ (H₂ shi)(Hshi)(shi)₇ (C₅ H₅ N)] (Ln-1; shi^3- =salicylhydroximate; Ln = Pr, Nd, Sm-Yb) has been synthesized and characterized. Ln-1 display both interesting magnetic and luminescent properties. Sm-1 has sharp emission bands in the visible and the near-infrared (NIR) regions with quantum yield values (QSmL ) of 1.64(9) and 5.5(2)^. 10^-2 %, respectively. Tb-1 exhibits a weak green emission (QTbL =1.89(3)^. 10^-1 %) while Pr-1, Nd-1, Ho-1, Er-1, and Yb-1 possess emission bands in the NIR range with QPrL =3.7(2)^. 10^-3 %, QNdL =1.71(5)^. 10^-1 %, QHoL =1.1(2)^. 10^-3 %, QErL =7.1(2)^. 10^-3 % and QYbL =0.65(3) %. Nd-1, Dy-1, and Yb-1 display slow magnetization relaxation in an applied field, where only Dy-1 has been observed to follow an Orbach process (U_eff =12.7 K). The combination of NIR emission with magnetic properties makes Nd-1 and Yb-1 attractive candidates as smart materials addressable in two manners.

Keywords: cryptands; lanthanides; luminescence; magnetic properties; spectroscopy.