[Re (L) (CO) (n+) ]複合体における補助リガンドを用いたILCT寿命の劇的な変化:統合されたスペクトロスコピックおよび理論的研究
Georgina E Shillito1, Thomas B J Hall1, Dan Preston1
1Department of Chemistry , University of Otago , P.O. Box 56 , Dunedin , New Zealand.
Journal of the American Chemical Society
|March 15, 2018
まとめ
補助リガンドは,レニウム複合体における興奮状態の寿命を大きく変化させ,2つの量位で変化する. この変動は,非放射性崩壊率と放射能を相関させるエネルギーギャップ法によって説明される.
科学分野:
- 無機化学
- フォト物理学
- スペクトロスコーピー
背景:
- レーニウムポリピリジル複合体は,光化学と光物理学において極めて重要です.
- 活性化状態のダイナミクスを理解することは 機能的な材料を設計する上で重要です
- イントラリガンド電荷伝送 (ILCT) 状態は光物理的性質に影響する.
研究 の 目的:
- fac-[Re(L) ((CO) 3 ((α-ダイミン) ]n+複合体の光物理学的性質を調査する.
- 興奮状態の生涯における補助連帯 (L) の役割を解明する.
- 電子的および構造的要因と相関する.
主な方法:
- 電子と振動スペクトル (一時的吸収,放出,TR2,TRIR) を利用した.
- 使用した量子化学方法 (TDDFT計算).
- 温度に依存した寿命測定を行った.
主要な成果:
- すべての研究された複合体に対して,発射状態を3ILCTとして特定した.
- 3ILCTの寿命 (6. 0μsから27ns) に2つの大きさの変化が観察されました.
- 非放射性崩壊率と 放射能エネルギーとの相関が 発見され エネルギーギャップの法則が 支持されました
結論:
- 補助結合体の選択は興奮状態の性質を変えることなく,興奮状態の寿命に大きな影響を与えます.
- エネルギーギャップ法は,観察された寿命の変動を効果的に説明します.
- これらの発見は,適合した光物理的性質を持つレニウム複合体の設計に関する洞察を提供します.
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