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ONIOM studies on thermally activated delayed fluorescence of copper(I) dimers in crystal.

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Title: ONIOM studies on thermally activated delayed fluorescence of copper(I) dimers in crystal.
Authors: Gao, Yuan-Jun1, Wang, Zi-Rui1, Chen, Wen-Kai1, Fang, Wei-Hai1, Cui, Ganglong1 ganglong.cui@bnu.edu.cn
Source: Chemical Physics. Nov2018, Vol. 515, p692-703. 12p.
Subjects: Delayed fluorescence, Excited states, Ground state (Quantum mechanics), Copper, Ligands (Chemistry), Dimers
Abstract: Graphical abstract Abstract Herein we have employed M06 and TD-M06 methods with the ONIOM approach to study the thermally activated delayed fluorescence (TADF) phenomenon of three halide-bridged Cu(I) dimers bearing amino-phosphane ligands in crystal (Cl-, Br-, and I-coordinated ones). On the basis of spectroscopic properties, ground- and excited-state geometric and electronic structures, and photophysical properties, we have found that the S 1 and T 1 states have a very small energy gap ▵ E S 1 - T 1 , less than 4.0 kcal/mol, which makes the forward and reverse intersystem crossing ISC and rISC processes between S 1 to T 1 very efficient and a population equilibrium can be established. The rISC rates are visibly sensitive to temperature and increasing temperature clearly enhances the rISC rates thus rationalizing experimentally observed TADF phenomenon. Moreover, we have also found that the low-frequency vibrational modes related to the torsional motion of the coordinated ligands have large Huang-Rhys factors, which increase from Cl via Br to I-coordinated Cu(I) dimers. In this varying process, the ISC rates increase visibly whereas the rISC rates change slightly. Our work provides useful microscopic knowledge to understand the TADF emission of the Cu(I) dimers, which could be helpful for the rational design of TADF materials with excellent performance. [ABSTRACT FROM AUTHOR]
Copyright of Chemical Physics is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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DbLabel: Engineering Source
An: 133498932
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  Data: ONIOM studies on thermally activated delayed fluorescence of copper(I) dimers in crystal.
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  Data: <searchLink fieldCode="AR" term="%22Gao%2C+Yuan-Jun%22">Gao, Yuan-Jun</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Wang%2C+Zi-Rui%22">Wang, Zi-Rui</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Chen%2C+Wen-Kai%22">Chen, Wen-Kai</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Fang%2C+Wei-Hai%22">Fang, Wei-Hai</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Cui%2C+Ganglong%22">Cui, Ganglong</searchLink><relatesTo>1</relatesTo><i> ganglong.cui@bnu.edu.cn</i>
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  Data: <searchLink fieldCode="JN" term="%22Chemical+Physics%22">Chemical Physics</searchLink>. Nov2018, Vol. 515, p692-703. 12p.
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  Data: <searchLink fieldCode="DE" term="%22Delayed+fluorescence%22">Delayed fluorescence</searchLink><br /><searchLink fieldCode="DE" term="%22Excited+states%22">Excited states</searchLink><br /><searchLink fieldCode="DE" term="%22Ground+state+%28Quantum+mechanics%29%22">Ground state (Quantum mechanics)</searchLink><br /><searchLink fieldCode="DE" term="%22Copper%22">Copper</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Dimers%22">Dimers</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Graphical abstract Abstract Herein we have employed M06 and TD-M06 methods with the ONIOM approach to study the thermally activated delayed fluorescence (TADF) phenomenon of three halide-bridged Cu(I) dimers bearing amino-phosphane ligands in crystal (Cl-, Br-, and I-coordinated ones). On the basis of spectroscopic properties, ground- and excited-state geometric and electronic structures, and photophysical properties, we have found that the S 1 and T 1 states have a very small energy gap ▵ E S 1 - T 1 , less than 4.0 kcal/mol, which makes the forward and reverse intersystem crossing ISC and rISC processes between S 1 to T 1 very efficient and a population equilibrium can be established. The rISC rates are visibly sensitive to temperature and increasing temperature clearly enhances the rISC rates thus rationalizing experimentally observed TADF phenomenon. Moreover, we have also found that the low-frequency vibrational modes related to the torsional motion of the coordinated ligands have large Huang-Rhys factors, which increase from Cl via Br to I-coordinated Cu(I) dimers. In this varying process, the ISC rates increase visibly whereas the rISC rates change slightly. Our work provides useful microscopic knowledge to understand the TADF emission of the Cu(I) dimers, which could be helpful for the rational design of TADF materials with excellent performance. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Chemical Physics is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1016/j.chemphys.2018.07.016
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      – Code: eng
        Text: English
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      – SubjectFull: Ground state (Quantum mechanics)
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      – SubjectFull: Copper
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      – SubjectFull: Dimers
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      – TitleFull: ONIOM studies on thermally activated delayed fluorescence of copper(I) dimers in crystal.
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              Text: Nov2018
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