Unravelling Mechanism of Crystallization-Induced Room Temperature Phosphorescence in Pure Organic Molecules from QM/MM calculations
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- 英文论文题名：Unravelling Mechanism of Crystallization-Induced Room Temperature Phosphorescence in Pure Organic Molecules from QM/MM calculations
- 论文作者：Huili Ma ; Wen Shi ; Jiajun Ren ; Wenqiang Li ; Qian Peng ; Zhigang Shuai
- 英文论文作者：Huili Ma ; Wen Shi ; Jiajun Ren ; Wenqiang Li ; Qian Peng ; Zhigang Shuai ; Key Laboratory of Organic Opto Electronics and Molecular Engineering ; Department of Chemistry ; Tsinghua University ; Key Laboratory of Organic Solids ; Beijing National Laboratory for Molecular Science(BNLMS) ; Institute of Chemistry ; Chinese Academy of Sciences
- 年：2016
- 作者机构：Key Laboratory of Organic Opto Electronics and Molecular Engineering,Department of Chemistry,Tsinghua University;Key Laboratory of Organic Solids,Beijing National Laboratory for Molecular Science(BNLMS),Institute of Chemistry,Chinese Academy of Sciences;
- 英文论文关键词：Persistent room temperature phosphorescence ; electrostatic interaction ; inverted states ; intersystem crossing
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十八分会：电子结构理论方法的发展与应用
- 语种：英文
- 分类号：O621.2
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十八分会 ; 电子结构理论方法的发展与应用
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：117k
- 原文格式：D
- 会议级别：全国
摘要
Exploring the origin of the purely organic room temperature phosphorescence is of prime importance and challenge.~(1-7) Here we unveiled the effect of crystallization on the luminescent properties of organic molecules through the combined quantum and molecular mechanics CASPT2/AMBER. Taking terephthalic acid~4 as an example, we found that the electrostatic interaction not only induced an enhanced radiative chancel of T_1→S_0 through the dipole-allowed S_1 state but also hindered the nonradiative decay process of the emissive states upon crystallization, resulting in the observed RTP. From gas to crystal, the S_1 state is inverted as ~1(ππ*) from ~1(nπ*) state with hugely increased transition dipole moment, generating efficacious radiative pathways to T_1→S_0, and then leading to boosted RTP based on unchanged nonradiative decay of triplet states. Moreover, the nonradiative decay is blocked by the restriction of the high-frequency C=O stretching vibration rather than the conventional low-frequency aromatic rotation in crystal.
Exploring the origin of the purely organic room temperature phosphorescence is of prime importance and challenge.~(1-7) Here we unveiled the effect of crystallization on the luminescent properties of organic molecules through the combined quantum and molecular mechanics CASPT2/AMBER.Taking terephthalic acid~4 as an example, we found that the electrostatic interaction not only induced an enhanced radiative chancel of T_1→S_0 through the dipole-allowed S_1 state but also hindered the nonradiative decay process of the emissive states upon crystallization, resulting in the observed RTP.From gas to crystal, the S_1 state is inverted as ~1(ππ*) from ~1(nπ*) state with hugely increased transition dipole moment, generating efficacious radiative pathways to T_1→S_0, and then leading to boosted RTP based on unchanged nonradiative decay of triplet states.Moreover, the nonradiative decay is blocked by the restriction of the high-frequency C=O stretching vibration rather than the conventional low-frequency aromatic rotation in crystal.
Exploring the origin of the purely organic room temperature phosphorescence is of prime importance and challenge.~(1-7) Here we unveiled the effect of crystallization on the luminescent properties of organic molecules through the combined quantum and molecular mechanics CASPT2/AMBER.Taking terephthalic acid~4 as an example, we found that the electrostatic interaction not only induced an enhanced radiative chancel of T_1→S_0 through the dipole-allowed S_1 state but also hindered the nonradiative decay process of the emissive states upon crystallization, resulting in the observed RTP.From gas to crystal, the S_1 state is inverted as ~1(ππ*) from ~1(nπ*) state with hugely increased transition dipole moment, generating efficacious radiative pathways to T_1→S_0, and then leading to boosted RTP based on unchanged nonradiative decay of triplet states.Moreover, the nonradiative decay is blocked by the restriction of the high-frequency C=O stretching vibration rather than the conventional low-frequency aromatic rotation in crystal.
引文
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[2]An,Z.;Zheng,C.;Tao,Y.;Chen,R.;Shi,H.;Chen,T.;Wang,Z.;Li,H.;Deng,R.;Liu,X.;Huang,W.Nature Mater.2015,14,685.
[3]Gong,Y.;Chen,G.;Peng,Q.;Yuan,W.Z.;Xie,Y.;Li,S.;Zhang,Y.;Tang,B.Z.Adv.Mater.2015,27,6195.
[4]Gong,Y.;Zhao,L.;Peng,Q.;Fan,D.;Yuan,W.Z.;Zhang,Y.;Tang,B.Z.Chemi.Sci.2015,6,4438.
[5]Ward,J.S.;Nobuyasu,R.S.;Batsanov,A.S.;Data,P.;Monkman,A.P.;Dias,F.B.;Bryce,M.R.Chem.Commun.2016,52,2612.
[6]Xue,P.;Wang,P.;Chen,P.;Yao,B.;Gong,P.;Sun,J.;Zhang,Z.;Lu,R.Chemi.Sci.2016,DOI:10.1039/C5SC03739E.
[7]Yang,Z.;Mao,Z.;Zhang,X.;Ou,D.;Mu,Y.;Zhang,Y.;Zhao,C.;Liu,S.;Chi,Z.;Xu,J.;Wu,Y.-C.;Lu,P.-Y.;Lien,A.;Bryce,M.R.Ange w.Chem.Int.Ed.2016,55,2181.