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

Abstract

In this paper 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 andmore » broadens the fundamental understanding of their ground and excited state properties.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1402055
Alternate Identifier(s):
OSTI ID: 1402497
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal Issue: 38; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kohler, Lars, Hadt, Ryan G., Hayes, Dugan, Chen, Lin X., Northwestern Univ., Evanston, IL, and Mulfort, Karen L. Synthesis, structure, and excited state kinetics of heteroleptic Cu(i) complexes with a new sterically demanding phenanthroline ligand. United States: N. p., 2017. Web. doi:10.1039/C7DT02476B.
Kohler, Lars, Hadt, Ryan G., Hayes, Dugan, Chen, Lin X., Northwestern Univ., Evanston, IL, & Mulfort, Karen L. Synthesis, structure, and excited state kinetics of heteroleptic Cu(i) complexes with a new sterically demanding phenanthroline ligand. United States. doi:10.1039/C7DT02476B.
Kohler, Lars, Hadt, Ryan G., Hayes, Dugan, Chen, Lin X., Northwestern Univ., Evanston, IL, and Mulfort, Karen L. Mon . "Synthesis, structure, and excited state kinetics of heteroleptic Cu(i) complexes with a new sterically demanding phenanthroline ligand". United States. doi:10.1039/C7DT02476B. https://www.osti.gov/servlets/purl/1402055.
@article{osti_1402055,
title = {Synthesis, structure, and excited state kinetics of heteroleptic Cu(i) complexes with a new sterically demanding phenanthroline ligand},
author = {Kohler, Lars and Hadt, Ryan G. and Hayes, Dugan and Chen, Lin X. and Northwestern Univ., Evanston, IL and Mulfort, Karen L.},
abstractNote = {In this paper 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.},
doi = {10.1039/C7DT02476B},
journal = {Dalton Transactions},
number = 38,
volume = 46,
place = {United States},
year = {2017},
month = {9}
}

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    Works referencing / citing this record:

    Functional Porous Coordination Polymers
    journal, April 2004

    • Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro
    • Angewandte Chemie International Edition, Vol. 43, Issue 18, p. 2334-2375
    • DOI: 10.1002/anie.200300610

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    journal, January 1912


    Synthesis of a Bis-macrocycle Containing Two Back-to-Back Rigidly Connected 1,10-Phenanthroline Units as a Central Core and its Incorporation in a Handcuff-Like Catenane
    journal, September 2007

    • Frey, Julien; Kraus, Tomáš; Heitz, Valérie
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    • DOI: 10.1002/chem.200700671

    Über die raumisomeren Kobaltverbindungen
    journal, January 1912


    Quantum chemical calculations of the reorganization energy of blue-copper proteins
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    • Olsson, Mats H. M.; Ryde, Ulf; Roos, Björn O.
    • Protein Science, Vol. 7, Issue 12
    • DOI: 10.1002/pro.5560071220

    Copper coordination in blue proteins
    journal, October 2000

    • Gray, Harry B.; Malmström, Bo G.; Williams, R. J. P.
    • JBIC Journal of Biological Inorganic Chemistry, Vol. 5, Issue 5
    • DOI: 10.1007/s007750000146

    Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium(II) and its analogues
    journal, October 1982


    Exciplex quenching of photo-excitd copper complexes
    journal, May 1985


    Improving the photophysical properties of copper(I) bis(phenanthroline) complexes
    journal, December 2008

    • Laviecambot, A.; Cantuel, M.; Leydet, Y.
    • Coordination Chemistry Reviews, Vol. 252, Issue 23-24
    • DOI: 10.1016/j.ccr.2008.03.013

    Recent advances in understanding blue copper proteins
    journal, April 2011


    Interplays of excited state structures and dynamics in copper(I) diimine complexes: Implications and perspectives
    journal, January 2015

    • Mara, Michael W.; Fransted, Kelly A.; Chen, Lin X.
    • Coordination Chemistry Reviews, Vol. 282-283
    • DOI: 10.1016/j.ccr.2014.06.013

    Time-resolved X-ray absorption spectroscopy for the study of molecular systems relevant for artificial photosynthesis
    journal, December 2015


    Heteroleptic bis-diimine copper(I) complexes for applications in solar energy conversion
    journal, January 2016


    Coordination geometry and bio-inspired ligands: useful concepts in homogeneous catalysis? A conceptual view
    journal, December 2004


    Advances in the light conversion properties of Cu(I)-based photosensitizers
    journal, November 2014


    Modular Homogeneous Chromophore–Catalyst Assemblies
    journal, April 2016


    Cuprous Phenanthroline MLCT Chromophore Featuring Synthetically Tailored Photophysics
    journal, September 2016


    Transient Absorption Dynamics of Sterically Congested Cu(I) MLCT Excited States
    journal, March 2015

    • Garakyaraghi, Sofia; Danilov, Evgeny O.; McCusker, Catherine E.
    • The Journal of Physical Chemistry A, Vol. 119, Issue 13
    • DOI: 10.1021/acs.jpca.5b00901

    Rational Design, Synthesis, Purification, and Activation of Metal−Organic Framework Materials
    journal, August 2010

    • Farha, Omar K.; Hupp, Joseph T.
    • Accounts of Chemical Research, Vol. 43, Issue 8, p. 1166-1175
    • DOI: 10.1021/ar1000617

    Ultrafast Excited-State Dynamics of Copper(I) Complexes
    journal, February 2015

    • Iwamura, Munetaka; Takeuchi, Satoshi; Tahara, Tahei
    • Accounts of Chemical Research, Vol. 48, Issue 3
    • DOI: 10.1021/ar500353h

    Supramolecular Coordination Chemistry and Functional Microporous Molecular Materials
    journal, October 2001

    • Dinolfo, Peter H.; Hupp, Joseph T.
    • Chemistry of Materials, Vol. 13, Issue 10
    • DOI: 10.1021/cm010176f

    Electronic Structures of Metal Sites in Proteins and Models:  Contributions to Function in Blue Copper Proteins
    journal, February 2004

    • Solomon, Edward I.; Szilagyi, Robert K.; DeBeer George, Serena
    • Chemical Reviews, Vol. 104, Issue 2
    • DOI: 10.1021/cr0206317

    Recent Developments in the Preparation and Chemistry of Metallacycles and Metallacages via Coordination
    journal, March 2015

    • Cook, Timothy R.; Stang, Peter J.
    • Chemical Reviews, Vol. 115, Issue 15
    • DOI: 10.1021/cr5005666

    Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis
    journal, June 1977


    Chemical Redox Agents for Organometallic Chemistry
    journal, January 1996

    • Connelly, Neil G.; Geiger, William E.
    • Chemical Reviews, Vol. 96, Issue 2
    • DOI: 10.1021/cr940053x

    Steric influences on the photoluminescence from copper(I) phenanthrolines in rigid media
    journal, February 1991

    • Everly, R. Michael.; Ziessel, Raymond.; Suffert, Jean.
    • Inorganic Chemistry, Vol. 30, Issue 3
    • DOI: 10.1021/ic00003a041

    Time-resolved resonance Raman spectroscopy of bis(2,9-dimethyl-1,10-phenanthroline)copper(1+) in solution
    journal, July 1991

    • Gordon, Keith C.; McGarvey, John J.
    • Inorganic Chemistry, Vol. 30, Issue 15
    • DOI: 10.1021/ic00015a008

    Photodriven Energy Transfer from Cuprous Phenanthroline Derivatives
    journal, January 1995

    • Castellano, Felix N.; Ruthkosky, Mark; Meyer, Gerald J.
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