Effective Photosensitization in Excited-State Equilibrium: Brilliant Luminescence of TbIII Coordination Polymers Through Ancillary Ligand Modifications

Yuichi Kitagawa; Ryoma Moriake; Tomoko Akama; Koki Saito; Kota Aikawa; Sunao Shoji; Koji Fushimi; Masato Kobayashi; Tetsuya Taketsugu; Yasuchika Hasegawa

doi:10.1002/cplu.202200151

Effective Photosensitization in Excited-State Equilibrium: Brilliant Luminescence of Tb^III Coordination Polymers Through Ancillary Ligand Modifications

Chempluschem. 2022 Oct;87(10):e202200151. doi: 10.1002/cplu.202200151. Epub 2022 Jul 13.

Authors

Yuichi Kitagawa^{1

2}, Ryoma Moriake³, Tomoko Akama^{2

4}, Koki Saito³, Kota Aikawa³, Sunao Shoji^{1

2}, Koji Fushimi¹, Masato Kobayashi^{2

4}, Tetsuya Taketsugu^{2

4}, Yasuchika Hasegawa^{1

2}

Affiliations

¹ Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku Sapporo, Hokkaido, 060-8628, Japan.
² Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku Sapporo, Hokkaido, 001-0021, Japan.
³ Graduate School of Chemical Sciences and Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku Sapporo, Hokkaido, 060-8628, Japan.
⁴ Faculty of Science, Hokkaido University, Kita 10, Nishi 8, Kita-ku Sapporo, Hokkaido, 060-0810, Japan.

PMID: 35822663
DOI: 10.1002/cplu.202200151

Abstract

Molecular photosensitizers provide efficient light-absorbing abilities for photo-functional materials. Herein, effective photosensitization in excited-state equilibrium is demonstrated using five Tb^III coordination polymers. The coordination polymers are composed of Tb^III ions (emission center), hexafluoroacetylacetonato (photosensitizer ligands), and phosphine oxide-based bridges (ancillary ligands). The two types of ligand combinations induces a rigid coordination structure via intermolecular interactions, resulting in high thermal stability (with decomposition temperatures above 300 °C). Excited-triplet-state lifetimes of photosensitizer ligands (τ=120-1320 μs) are strongly dependent on the structure of the ancillary ligands. The photosensitizer with a long excited-triplet-state lifetime (τ≥1120 μs) controls the excited state equilibrium between the photosensitizer and Tb^III , allowing the construction of Tb^III coordination polymer with high Tb^III emission quantum yield (≥70 %).

Keywords: energy transfer; luminescence; photosensitizer; terbium; triplet state.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Ions
Ligands
Luminescence*
Oxides
Photosensitizing Agents* / chemistry
Polymers / chemistry

Substances

Ions
Ligands
Oxides
Photosensitizing Agents
Polymers