External Heavy-Atom Effect via Orbital Interactions Revealed by Single-Crystal X-ray Diffraction

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• 作者：Xingxing Sun ; Baicheng Zhang ; Xinyang Li ; Carl O. Trindle ; Guoqing Zhang
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：July 28, 2016
• 年：2016
• 卷：120
• 期：29
• 页码：5791-5797
• 全文大小：492K
• 年卷期：0
• ISSN：1520-5215

文摘

Enhanced spin–orbit coupling through external heavy-atom effect (EHE) has been routinely used to induce room-temperature phosphorescence (RTP) for purely organic molecular materials. Therefore, understanding the nature of EHE, i.e., the specific orbital interactions between the external heavy atom and the luminophore, is of essential importance in molecular design. For organic systems, halogens (e.g., Cl, Br, and I) are the most commonly seen heavy atoms serving to realize the EHE-related RTP. In this report, we conduct an investigation on how heavy-atom perturbers and aromatic luminophores interact on the basis of data obtained from crystallography. We synthesized two classes of molecular systems including N-haloalkyl-substituted carbazoles and quinolinium halides, where the luminescent molecules are considered as “base” or “acid” relative to the heavy-atom perturbers, respectively. We propose that electron donation from a π molecular orbital (MO) of the carbazole to the σ* MO of the C–X bond (π/σ*) and n electron donation to a π* MO of the quinolinium moiety (n/π*) are responsible for the EHE (RTP) in the solid state, respectively.