Europium and Terbium Coordination
Polymers Assembled
from Hexacarboxylate Ligands: Structures and Luminescent Properties
Yanli Gai
Feilong Jiang
Lian Chen
Mingyan Wu
Kongzhao Su
Jie Pan
Xiuyan Wan
Maochun Hong
10.1021/cg401452p.s002
https://acs.figshare.com/articles/dataset/Europium_and_Terbium_Coordination_Polymers_Assembled_from_Hexacarboxylate_Ligands_Structures_and_Luminescent_Properties/2317810
Six lanthanide coordination polymers
of the formula [Ln(L<sup>1</sup>)<sub>0.5</sub>(H<sub>2</sub>O)<sub>2</sub>]·2H<sub>2</sub>O
[where Ln<sup>3+</sup>: Eu<sup>3+</sup> (<b>1</b>), Tb<sup>3+</sup> (<b>2</b>), and Gd<sup>3+</sup>(<b>3</b>)] and [Me<sub>2</sub>NH<sub>2</sub>][Ln(H<sub>2</sub>L<sup>2</sup>)(H<sub>2</sub>O)<sub>4</sub>]·0.5DMF·<i>x</i>H<sub>2</sub>O
[where Ln<sup>3+</sup>: Eu<sup>3+</sup> (<b>4</b>), Tb<sup>3+</sup> (<b>5</b>), and Gd<sup>3+</sup>(<b>6</b>)], based on <i>p</i>-terphenyl-2,2″,2‴,5,5″,5‴-hexacarboxylate
acid (H<sub>6</sub>L<sup>1</sup>), and <i>p</i>-terphenyl-3,2″,3″,5,5″,5‴,-hexacarboxylate
acid (H<sub>6</sub>L<sup>2</sup>), have been solvothermally synthesized
and structurally characterized. Complexes <b>1</b>–<b>3</b> are 3D frameworks exhibiting 6-connected pcu alpha-Po primitive
cubic network with topology (4<sup>12</sup>.6<sup>3</sup>), while
complexes <b>4</b>–<b>6</b> show two-dimensional
(2D) architectures showing simplified 3,4-connected binodal net and
(4.6<sup>2</sup>)(4<sup>2</sup>.6<sup>2</sup>.8<sup>2</sup>) topology.
Detailed photophysical behaviors have been explored on Eu<sup>3+</sup>, Tb<sup>3+</sup>, and Gd<sup>3+</sup> complexes. The calculated
triplet state energies of H<sub>6</sub>L<sup>1</sup> and H<sub>6</sub>L<sup>2</sup> lie above the emissive levels of Eu<sup>3+</sup> or
Tb<sup>3+</sup> in an ideal range for sensitizing. Furthermore, it
is demonstrated that the optimum energy gap between the triplet state
of ligand H<sub>6</sub>L<sup>1</sup> and the emissive level of Tb<sup>3+</sup> ion makes the overall quantum yield of Tb<sup>3+</sup> complex
(<b>2</b>) larger than its corresponding Eu<sup>3+</sup> complex
(<b>1</b>). In addition, the coordinated water in the inner
sphere has a significant negative influence on the overall quantum
yield, especially for the Eu<sup>3+</sup> complex (<b>4</b>)
compared to the Tb<sup>3+</sup> complex (<b>5</b>), due to the
deactivation process caused by vibrational OH oscillators.
2014-03-05 00:00:00
Luminescent PropertiesSix lanthanide coordination polymers
Terbium Coordination Polymers Assembled
H 6L
triplet state energies
vibrational OH oscillators
Gd
3 D frameworks
Eu
2NH
ligand H 6L
Ln
Tb