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Title: Bulky and Stable Copper(I)-Phenanthroline Complex: Impact of Steric Strain and Symmetry on the Excited-State Properties

Abstract

The steric strain around copper(I) in typical [Cu(NNR)2]+ complexes, where NNR is a diimine ligand substituted in α-positions of the nitrogen atoms by R, is known to strongly impact the excited-state properties. Generally speaking, the larger the R, the longer the emission lifetime and the higher the quantum yield. However, the stability of the coordination scaffold can be at stake if the steric strain imposed by R is too large. In this work, we explore a way of fine-tuning the steric strain around Cu(I) to reach a balance between high emission quantum yield and stability in a highly bulky copper(I) complex. Taking stable [Cu(dipp)2]+ and unstable [Cu(dtbp)2]+ (where dipp and dtbp are, respectively, 2,9- diisopropyl-1,10-phenanthroline and 2,9-di-tert-butyl-1,10-phenanthroline) as the boundary of two least and most sterically strained structures, we designed and characterized the nonsymmetrical ligand 2-isopropyl-9-tert-butyl-1,10-phenanthroline (L1) and corresponding complex [Cu(L1)2]+ (Cu1). The key experimental findings are that Cu1 exhibits a rigid tetrahedral geometry in the ground state, close to that of [Cu(dtbp)2]+ and with an intermediate stability between that of [Cu(dipp)2]+ and [Cu(dtbp)2]+. Conversely, the nonsymmetrical nature of ligand L1 leads to a shorter emission lifetime and smaller quantum yield than those of either [Cu(dipp)2]+ or [Cu(dtbp)2]+. This peculiarmore » behavior is rationalized through the in depth analysis of the ultrafast dynamics of the excited state measured with optical transient absorption spectroscopy and theoretical calculations performed on the ground and excited state of Cu1. Our main findings are that the obtained complex is significantly more stable than [Cu(dtbp)2]+ despite the sterically strained coordination sphere. The nonsymmetrical nature of the ligand translates into a strongly distorted structure in the excited state. The distortion can be described as a rocking motion of one ligand, entailing the premature extinction of the excited state via several deactivation channels.« less

Authors:
 [1];  [2]; ORCiD logo [2];  [3];  [1];  [4];  [5]; ORCiD logo [1]
+ Show Author Affiliations
  1. Université de Nantes, CNRS, CEISAM UMR6230, F-44000 Nantes, France
  2. Chemical Science and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
  3. Université de Rennes CNRS, Institut des Sciences Chimiques de Rennes, UMR6226, F-35000 Rennes, France
  4. Laboratoire de Chimie Quantique Institut de Chimie UMR 7177 CNRS-Université de Strasbourg, 4, Rue Blaise Pascal CS 90032, F-67081 Strasbourg Cedex, France
  5. Chemical Science and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States, Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
Publication Date:
Research Org.:
Univ. de Nantes (France). Chimie et Interdisciplinarite Synthese Analyse Modelisation (CEISAM); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1866307
Alternate Identifier(s):
OSTI ID: 1868026
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Name: Inorganic Chemistry Journal Volume: 61 Journal Issue: 19; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gimeno, Lea, Phelan, Brian T., Sprague-Klein, Emily A., Roisnel, Thierry, Blart, Errol, Gourlaouen, Christophe, Chen, Lin X., and Pellegrin, Yann. Bulky and Stable Copper(I)-Phenanthroline Complex: Impact of Steric Strain and Symmetry on the Excited-State Properties. United States: N. p., 2022. Web. doi:10.1021/acs.inorgchem.1c03901.
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Gimeno, Lea, Phelan, Brian T., Sprague-Klein, Emily A., Roisnel, Thierry, Blart, Errol, Gourlaouen, Christophe, Chen, Lin X., & Pellegrin, Yann. Bulky and Stable Copper(I)-Phenanthroline Complex: Impact of Steric Strain and Symmetry on the Excited-State Properties. United States. https://doi.org/10.1021/acs.inorgchem.1c03901
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Gimeno, Lea, Phelan, Brian T., Sprague-Klein, Emily A., Roisnel, Thierry, Blart, Errol, Gourlaouen, Christophe, Chen, Lin X., and Pellegrin, Yann. Wed . "Bulky and Stable Copper(I)-Phenanthroline Complex: Impact of Steric Strain and Symmetry on the Excited-State Properties". United States. https://doi.org/10.1021/acs.inorgchem.1c03901.
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@article{osti_1866307,
title = {Bulky and Stable Copper(I)-Phenanthroline Complex: Impact of Steric Strain and Symmetry on the Excited-State Properties},
author = {Gimeno, Lea and Phelan, Brian T. and Sprague-Klein, Emily A. and Roisnel, Thierry and Blart, Errol and Gourlaouen, Christophe and Chen, Lin X. and Pellegrin, Yann},
abstractNote = {The steric strain around copper(I) in typical [Cu(NNR)2]+ complexes, where NNR is a diimine ligand substituted in α-positions of the nitrogen atoms by R, is known to strongly impact the excited-state properties. Generally speaking, the larger the R, the longer the emission lifetime and the higher the quantum yield. However, the stability of the coordination scaffold can be at stake if the steric strain imposed by R is too large. In this work, we explore a way of fine-tuning the steric strain around Cu(I) to reach a balance between high emission quantum yield and stability in a highly bulky copper(I) complex. Taking stable [Cu(dipp)2]+ and unstable [Cu(dtbp)2]+ (where dipp and dtbp are, respectively, 2,9- diisopropyl-1,10-phenanthroline and 2,9-di-tert-butyl-1,10-phenanthroline) as the boundary of two least and most sterically strained structures, we designed and characterized the nonsymmetrical ligand 2-isopropyl-9-tert-butyl-1,10-phenanthroline (L1) and corresponding complex [Cu(L1)2]+ (Cu1). The key experimental findings are that Cu1 exhibits a rigid tetrahedral geometry in the ground state, close to that of [Cu(dtbp)2]+ and with an intermediate stability between that of [Cu(dipp)2]+ and [Cu(dtbp)2]+. Conversely, the nonsymmetrical nature of ligand L1 leads to a shorter emission lifetime and smaller quantum yield than those of either [Cu(dipp)2]+ or [Cu(dtbp)2]+. This peculiar behavior is rationalized through the in depth analysis of the ultrafast dynamics of the excited state measured with optical transient absorption spectroscopy and theoretical calculations performed on the ground and excited state of Cu1. Our main findings are that the obtained complex is significantly more stable than [Cu(dtbp)2]+ despite the sterically strained coordination sphere. The nonsymmetrical nature of the ligand translates into a strongly distorted structure in the excited state. The distortion can be described as a rocking motion of one ligand, entailing the premature extinction of the excited state via several deactivation channels.},
doi = {10.1021/acs.inorgchem.1c03901},
journal = {Inorganic Chemistry},
number = 19,
volume = 61,
place = {United States},
year = {Wed May 04 00:00:00 EDT 2022},
month = {Wed May 04 00:00:00 EDT 2022}
}
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