コバルト・ポルフィリン・チアジル・ラジカル・コーディネーション・ポリマー: 金属・有機電子
Delia A Haynes1, Laura J van Laeren1, Orde Q Munro2
1Department of Chemistry and Polymer Science, Stellenbosch University , Private Bag X1, Matieland 7602, South Africa.
Journal of the American Chemical Society
|September 20, 2017
まとめ
この研究では,コバルトテトラフェニルポルフィリンとpy-DTDA基から形成された新しい一次元調整ポリマー (CP) の詳細が示されています. CPは断片的な電子移転とユニークな共鳴ハイブリッド構造を示し,電子デバイスの可能性を示唆しています.
科学分野:
- 協調化学
- 材料科学
- オーガニックの電子機器
背景:
- コーディネーションポリマー (CP) は,調節可能な電子特性を提供します.
- 金属イオンと有機ラジカルの組み合わせは 新しい電子材料の機会をもたらします
- コバルトテトラフェニルポルフィリン (Co(TPP)) とpY-DTDAラジカルは,材料研究における既知の成分である.
研究 の 目的:
- Co ((TPP)) と py-DTDA を使って新しい一次元調整ポリマー (CP 3) を合成し,特徴づけること.
- 結果のCPの電子構造と結合特性を調査する.
- 電子機器におけるこのCPの潜在的応用を探求する.
主な方法:
- S=1/2 Co(TPP) と S=1/2 4-(4'-ピリジル) -1,2,3,5-ディチアジアゾリル (py-DTDA) 基から一次元調整ポリマー (CP 3) を合成する.
- 構造と電子の性質を決定するために,X線結晶学とスペクトル分析を行う.
- 電子状態と帯域構造をモデル化するための密度関数理論 (DFT) の計算.
主要な成果:
- 異常に長いS−S結合を特徴とする新しい一次元協調ポリマー (CP 3) が成功裏に合成されました.
- この結合は, [Co(TPP) ]0.5+ と py-DTDA0.5- と表記された整数以外の酸化還元状態を含んでいる.
- DFTの計算では,金属からリガンドへの電荷移転 (MLCT) と,十分な長さのオリゴマーには0.669 ((6) eVの帯域ギャップが明らかになった.
- 異なる溶媒条件により,異なる種が生じた:二磁性S結合アダクト (3a),二磁性N結合複合体 (3b),およびDMSOにおける紫色のCo (III) 複合体.
結論:
- 合成されたCPは,小数値電子移転と共振ハイブリッド結合によりユニークな電子特性を示しています.
- この材料は,計算された帯域構造と状態の密度によって,電子機器への応用が有望であることが示されています.
- この研究は,Co ((TPP) とpy-DTDAが機能的調整ポリマーを作成する際の汎用性を強調しています.
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