10.1021/acs.cgd.7b00400.s001
Rami J. Batrice
Rami J.
Batrice
Alyssa K. Adcock
Alyssa K.
Adcock
Paula M. Cantos
Paula M.
Cantos
Jeffery A. Bertke
Jeffery A.
Bertke
Karah E. Knope
Karah E.
Knope
Synthesis and Characterization
of an Isomorphous Lanthanide-Thiophenemonocarboxylate
Series (Ln = La–Lu, except Pm) Amenable to Color Tuning
American Chemical Society
2017
Single crystal X-ray diffraction studies
4 f block
coordination sphere TC anion
NIR
Ln metal centers
La -2
HTC
link LnO 8
H 2 O
14 lanthanide compounds
Solid-state fluorescence studies show ligand
1 D chains
Isomorphous Lanthanide-Thiophenemonocarboxylate Series
2017-07-31 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Synthesis_and_Characterization_of_an_Isomorphous_Lanthanide-Thiophenemonocarboxylate_Series_Ln_La_Lu_except_Pm_Amenable_to_Color_Tuning/5311390
A series
of 14 lanthanide compounds bearing 2-thiophenecarboxylate
(TC) have been prepared under aqueous conditions and structurally
characterized. Single crystal X-ray diffraction studies reveal a full
isomorphous series across the 4f block of the general formula [(Ln(TC)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>)·(HPy·TC)]<sub><i>n</i></sub>, (Ln = La (<b>La-1</b>) – Lu (<b>Lu-1</b>), excluding Pm), with observable contraction of the cell
volume and average metal–oxygen bond distances occurring when
moving from lanthanum to lutetium. The 8-coordinate Ln metal centers
are bound to two water molecules as well as six oxygen atoms from
one bidentate and four bridging TC units that link LnO<sub>8</sub> structural units into 1D chains. One lattice stabilizing pyridinium
and one outer coordination sphere TC anion are present per formula
unit. Reaction optimization provided moderate to high yields of the
title products; a lanthanum byproduct [La(TC)<sub>3</sub>(HTC)<sub>2</sub>]<sub><i>n</i></sub> (<b>La-2</b>) was formed
by performing the reaction at reduced temperature, or alternatively,
successive grinding of <b>La-1</b> in ethanol resulted in partial
conversion to <b>La-2</b>. Solid-state fluorescence studies
show ligand sensitized metal-based emission for Eu(III), Tb(III),
and Dy(III) in the visible region, and Nd(III) and Er(III) in the
NIR. Color tuning was easily achieved by varying europium:terbium
metal ratios in the reaction mixtures.