Intriguing Effects of Halogen Substitution on the Photophysical Properties of 2,9-(Bis)halo-Substituted Phenanthrolinecopper(I) Complexes
Three new copper(I) complexes [Cu(L ) ] (PF ) (where L stands for 2,9-dihalo-1,10-phenanthroline and X = Cl, Br, and I) have been synthesized in order to study the impact of halogen substituents tethered in the α position of the chelating nitrogen atoms on their physical properties. The photophysica...
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| Published in: | Inorganic chemistry Vol. 58; no. 12; p. 7730 |
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| Main Authors: | , , , , , , , , , , , , |
| Format: | Journal Article |
| Language: | English |
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17.06.2019
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| ISSN: | 1520-510X, 1520-510X |
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| Abstract | Three new copper(I) complexes [Cu(L
)
]
(PF
) (where L
stands for 2,9-dihalo-1,10-phenanthroline and X = Cl, Br, and I) have been synthesized in order to study the impact of halogen substituents tethered in the α position of the chelating nitrogen atoms on their physical properties. The photophysical properties of these new complexes (hereafter named Cu-X) were characterized in both their ground and excited states. Femtosecond ultrafast spectroscopy revealed that early photoinduced processes are faster for Cu-I than for Cu-Cl or Cu-Br, both showing similar behaviors. Their electronic absorption and electrochemical properties are comparable to benchmark [Cu(dmp)
]
(where dmp stands for 2,9-dimethyl-1,10-phenanthroline); furthermore, their optical features were fully reproduced by time-dependent density functional theory and ab initio molecular dynamics calculations. All three complexes are luminescent at room temperature, showing that halogen atoms bound to positions 2 and 9 of phenanthroline are sufficiently bulky to prevent strong interactions between the excited Cu complexes and solvent molecules in the coordination sphere. Their behavior in the excited state, more specifically the extent of the photoluminescence efficiency and its dependence on the temperature, is, however, strongly dependent on the nature of the halogen. A combination of ultrafast transient absorption spectroscopy, temperature-dependent steady-state fluorescence spectroscopy, and computational chemistry allows one to gain a deeper understanding of the behavior of all three complexes in their excited state. |
|---|---|
| AbstractList | Three new copper(I) complexes [Cu(L
)
]
(PF
) (where L
stands for 2,9-dihalo-1,10-phenanthroline and X = Cl, Br, and I) have been synthesized in order to study the impact of halogen substituents tethered in the α position of the chelating nitrogen atoms on their physical properties. The photophysical properties of these new complexes (hereafter named Cu-X) were characterized in both their ground and excited states. Femtosecond ultrafast spectroscopy revealed that early photoinduced processes are faster for Cu-I than for Cu-Cl or Cu-Br, both showing similar behaviors. Their electronic absorption and electrochemical properties are comparable to benchmark [Cu(dmp)
]
(where dmp stands for 2,9-dimethyl-1,10-phenanthroline); furthermore, their optical features were fully reproduced by time-dependent density functional theory and ab initio molecular dynamics calculations. All three complexes are luminescent at room temperature, showing that halogen atoms bound to positions 2 and 9 of phenanthroline are sufficiently bulky to prevent strong interactions between the excited Cu complexes and solvent molecules in the coordination sphere. Their behavior in the excited state, more specifically the extent of the photoluminescence efficiency and its dependence on the temperature, is, however, strongly dependent on the nature of the halogen. A combination of ultrafast transient absorption spectroscopy, temperature-dependent steady-state fluorescence spectroscopy, and computational chemistry allows one to gain a deeper understanding of the behavior of all three complexes in their excited state. Three new copper(I) complexes [Cu(LX)2]+(PF6-) (where LX stands for 2,9-dihalo-1,10-phenanthroline and X = Cl, Br, and I) have been synthesized in order to study the impact of halogen substituents tethered in the α position of the chelating nitrogen atoms on their physical properties. The photophysical properties of these new complexes (hereafter named Cu-X) were characterized in both their ground and excited states. Femtosecond ultrafast spectroscopy revealed that early photoinduced processes are faster for Cu-I than for Cu-Cl or Cu-Br, both showing similar behaviors. Their electronic absorption and electrochemical properties are comparable to benchmark [Cu(dmp)2]+ (where dmp stands for 2,9-dimethyl-1,10-phenanthroline); furthermore, their optical features were fully reproduced by time-dependent density functional theory and ab initio molecular dynamics calculations. All three complexes are luminescent at room temperature, showing that halogen atoms bound to positions 2 and 9 of phenanthroline are sufficiently bulky to prevent strong interactions between the excited Cu complexes and solvent molecules in the coordination sphere. Their behavior in the excited state, more specifically the extent of the photoluminescence efficiency and its dependence on the temperature, is, however, strongly dependent on the nature of the halogen. A combination of ultrafast transient absorption spectroscopy, temperature-dependent steady-state fluorescence spectroscopy, and computational chemistry allows one to gain a deeper understanding of the behavior of all three complexes in their excited state.Three new copper(I) complexes [Cu(LX)2]+(PF6-) (where LX stands for 2,9-dihalo-1,10-phenanthroline and X = Cl, Br, and I) have been synthesized in order to study the impact of halogen substituents tethered in the α position of the chelating nitrogen atoms on their physical properties. The photophysical properties of these new complexes (hereafter named Cu-X) were characterized in both their ground and excited states. Femtosecond ultrafast spectroscopy revealed that early photoinduced processes are faster for Cu-I than for Cu-Cl or Cu-Br, both showing similar behaviors. Their electronic absorption and electrochemical properties are comparable to benchmark [Cu(dmp)2]+ (where dmp stands for 2,9-dimethyl-1,10-phenanthroline); furthermore, their optical features were fully reproduced by time-dependent density functional theory and ab initio molecular dynamics calculations. All three complexes are luminescent at room temperature, showing that halogen atoms bound to positions 2 and 9 of phenanthroline are sufficiently bulky to prevent strong interactions between the excited Cu complexes and solvent molecules in the coordination sphere. Their behavior in the excited state, more specifically the extent of the photoluminescence efficiency and its dependence on the temperature, is, however, strongly dependent on the nature of the halogen. A combination of ultrafast transient absorption spectroscopy, temperature-dependent steady-state fluorescence spectroscopy, and computational chemistry allows one to gain a deeper understanding of the behavior of all three complexes in their excited state. |
| Author | Riobé, François Gimeno, Lea Daniel, Chantal Brown-Xu, Samantha Fumanal, Maria Pellegrin, Yann Quatela, Alessia Gourlaouen, Christophe Thobie-Gautier, Christine Planchat, Aurélien Chen, Lin X Blart, Errol Monnereau, Cyrille |
| Author_xml | – sequence: 1 givenname: Samantha surname: Brown-Xu fullname: Brown-Xu, Samantha organization: Department of Chemistry , Northwestern University , Evanston , Illinois 60208 , United States – sequence: 2 givenname: Maria orcidid: 0000-0002-4175-8876 surname: Fumanal fullname: Fumanal, Maria organization: Laboratoire de Chimie Quantique Institut de Chimie , UMR 7177, CNRS, Université de Strasbourg , 4 rue Blaise Pascal, CS 90032 , F-67081 Strasbourg Cedex , France – sequence: 3 givenname: Christophe surname: Gourlaouen fullname: Gourlaouen, Christophe organization: Laboratoire de Chimie Quantique Institut de Chimie , UMR 7177, CNRS, Université de Strasbourg , 4 rue Blaise Pascal, CS 90032 , F-67081 Strasbourg Cedex , France – sequence: 4 givenname: Lea surname: Gimeno fullname: Gimeno, Lea organization: Chimie Et Interdisciplinarité: Synthèse, Analyse, Modélisation (CEISAM) , UMR 6230, CNRS, Université UNAM , 2 rue de la Houssinière, BP 92208 , 44322 Nantes Cedex 3 , France – sequence: 5 givenname: Alessia surname: Quatela fullname: Quatela, Alessia organization: Horiba France SAS , Avenue de la Vauve, Passage Jobin Yvon CS 45002 , 91120 Palaiseau , France – sequence: 6 givenname: Christine surname: Thobie-Gautier fullname: Thobie-Gautier, Christine organization: Chimie Et Interdisciplinarité: Synthèse, Analyse, Modélisation (CEISAM) , UMR 6230, CNRS, Université UNAM , 2 rue de la Houssinière, BP 92208 , 44322 Nantes Cedex 3 , France – sequence: 7 givenname: Errol surname: Blart fullname: Blart, Errol organization: Chimie Et Interdisciplinarité: Synthèse, Analyse, Modélisation (CEISAM) , UMR 6230, CNRS, Université UNAM , 2 rue de la Houssinière, BP 92208 , 44322 Nantes Cedex 3 , France – sequence: 8 givenname: Aurélien surname: Planchat fullname: Planchat, Aurélien organization: Chimie Et Interdisciplinarité: Synthèse, Analyse, Modélisation (CEISAM) , UMR 6230, CNRS, Université UNAM , 2 rue de la Houssinière, BP 92208 , 44322 Nantes Cedex 3 , France – sequence: 9 givenname: François orcidid: 0000-0001-6746-8132 surname: Riobé fullname: Riobé, François organization: Laboratoire de Chimie, ENS de Lyon , UMR 5182, CNRS, Université de Lyon , F69342 Lyon , France – sequence: 10 givenname: Cyrille orcidid: 0000-0002-8928-2416 surname: Monnereau fullname: Monnereau, Cyrille organization: Laboratoire de Chimie, ENS de Lyon , UMR 5182, CNRS, Université de Lyon , F69342 Lyon , France – sequence: 11 givenname: Lin X surname: Chen fullname: Chen, Lin X organization: Chemical Sciences and Engineering Division , Argonne National Laboratory , Lemont , Illinois 60439 , United States – sequence: 12 givenname: Chantal orcidid: 0000-0002-0520-2969 surname: Daniel fullname: Daniel, Chantal organization: Laboratoire de Chimie Quantique Institut de Chimie , UMR 7177, CNRS, Université de Strasbourg , 4 rue Blaise Pascal, CS 90032 , F-67081 Strasbourg Cedex , France – sequence: 13 givenname: Yann orcidid: 0000-0003-0006-0815 surname: Pellegrin fullname: Pellegrin, Yann organization: Chimie Et Interdisciplinarité: Synthèse, Analyse, Modélisation (CEISAM) , UMR 6230, CNRS, Université UNAM , 2 rue de la Houssinière, BP 92208 , 44322 Nantes Cedex 3 , France |
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| Snippet | Three new copper(I) complexes [Cu(L
)
]
(PF
) (where L
stands for 2,9-dihalo-1,10-phenanthroline and X = Cl, Br, and I) have been synthesized in order to study... Three new copper(I) complexes [Cu(LX)2]+(PF6-) (where LX stands for 2,9-dihalo-1,10-phenanthroline and X = Cl, Br, and I) have been synthesized in order to... |
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| Title | Intriguing Effects of Halogen Substitution on the Photophysical Properties of 2,9-(Bis)halo-Substituted Phenanthrolinecopper(I) Complexes |
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