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Synthesis, structure, and excited state kinetics of heteroleptic Cu(I) complexes with a new sterically demanding phenanthroline ligand

Kohler, Lars and Hadt, Ryan G. and Hayes, Dugan and Chen, Lin X. and Mulfort, Karen L. (2017) Synthesis, structure, and excited state kinetics of heteroleptic Cu(I) complexes with a new sterically demanding phenanthroline ligand. Dalton Transactions, 46 (38). pp. 13088-13100. ISSN 1477-9226. doi:10.1039/c7dt02476b.

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In this report we describe the synthesis of a new phenanthroline ligand, 2,9-di(2,4,6-tri-isopropyl-phenyl)-1,10-phenanthroline (bL2) and its use as the blocking ligand in the preparation of two new heteroleptic Cu(i)diimine complexes. Analysis of the CuHETPHEN single crystal structures shows a distinct distortion from an ideal tetrahedral geometry around the Cu(i) center, forced by the secondary phenanthroline ligand rotating to accommodate the isopropyl groups of bL2. The increased steric bulk of bL2 as compared to the more commonly used 2,9-dimesityl-1,10-phenanthroline blocking ligand prohibits intramolecular ligand-ligand interaction, which is unique among CuHETPHEN complexes. The ground state optical and redox properties of CuHETPHEN complexes are responsive to the substitution on the blocking ligand even though the differences in structure are far removed from the Cu(i) center. Transient optical spectroscopy was used to understand the excited state kinetics in both coordinating and non-coordinating solvents following visible excitation. Substitution of the blocking phenanthroline ligand has a significant impact on the ^3MLCT decay and can be used to increase the excited state lifetime by 50%. Electronic structure calculations established relationships between ground and excited state properties, and general entatic state concepts are discussed for copper photosensitizers. This work contributes to the growing library of CuHETPHEN complexes and broadens the fundamental understanding of their ground and excited state properties.

Item Type:Article
Related URLs:
URLURL TypeDescription
Hadt, Ryan G.0000-0001-6026-1358
Hayes, Dugan0000-0003-4171-5179
Chen, Lin X.0000-0002-8450-6687
Mulfort, Karen L.0000-0002-3132-1179
Additional Information:© The Royal Society of Chemistry 2017. Received 8th July 2017, Accepted 18th September 2017. First published on 25th September 2017. This work is supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grant DE-AC02-06CH11357. RGH acknowledges support from the ANL Enrico Fermi Fellowship and DH acknowledges support from the ANL Joseph J. Katz Fellowship. We thank Dr Richard E. Wilson for assistance in collecting the X-ray diffraction data. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract no. DE-AC02-06CH11357. We thank Dr David J. Gosztola for his expert assistance at the transient absorption facility at CNM. We gratefully acknowledge the computing resources provided on Blues and Fusion, both high-performance computing clusters operated by the Laboratory Computing Resource Center at ANL. There are no conflicts of interest to declare.
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-06CH11357
Argonne National LaboratoryUNSPECIFIED
Issue or Number:38
Record Number:CaltechAUTHORS:20180612-141349167
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87020
Deposited By: George Porter
Deposited On:12 Jun 2018 21:39
Last Modified:15 Nov 2021 20:44

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