skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions

Abstract

The first gold dipyrrin-bisphenolates have been synthesized. Like their corrole analogues, they exhibit Au III –L 3− ground states, providing rare innocent paradigms for a class of complexes that commonly occur as metalloradicals.

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry, UiT – The Arctic University of Norway, Tromsø N-9037, Norway
  2. Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB), UMR CNRS 6302, Université Bourgogne-Franche Comté, 21078 Dijon Cedex, France
  3. Department of Chemistry, UiT – The Arctic University of Norway, Tromsø N-9037, Norway, Department of Chemistry
  4. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1580767
Resource Type:
Published Article
Journal Name:
RSC Advances
Additional Journal Information:
Journal Name: RSC Advances Journal Volume: 10 Journal Issue: 1; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Thomas, Kolle E., Desbois, Nicolas, Conradie, Jeanet, Teat, Simon J., Gros, Claude P., and Ghosh, Abhik. Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions. United Kingdom: N. p., 2020. Web. doi:10.1039/C9RA09228E.
Thomas, Kolle E., Desbois, Nicolas, Conradie, Jeanet, Teat, Simon J., Gros, Claude P., & Ghosh, Abhik. Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions. United Kingdom. doi:10.1039/C9RA09228E.
Thomas, Kolle E., Desbois, Nicolas, Conradie, Jeanet, Teat, Simon J., Gros, Claude P., and Ghosh, Abhik. Thu . "Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions". United Kingdom. doi:10.1039/C9RA09228E.
@article{osti_1580767,
title = {Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions},
author = {Thomas, Kolle E. and Desbois, Nicolas and Conradie, Jeanet and Teat, Simon J. and Gros, Claude P. and Ghosh, Abhik},
abstractNote = {The first gold dipyrrin-bisphenolates have been synthesized. Like their corrole analogues, they exhibit Au III –L 3− ground states, providing rare innocent paradigms for a class of complexes that commonly occur as metalloradicals.},
doi = {10.1039/C9RA09228E},
journal = {RSC Advances},
number = 1,
volume = 10,
place = {United Kingdom},
year = {2020},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9RA09228E

Save / Share:

Works referenced in this record:

Metal complexes of corrole
journal, June 2019

  • Nardis, Sara; Mandoj, Federica; Stefanelli, Manuela
  • Coordination Chemistry Reviews, Vol. 388
  • DOI: 10.1016/j.ccr.2019.02.034

Red/Near-Infrared Luminescence Tuning of Group-14 Element Complexes of Dipyrrins Based on a Central Atom
journal, January 2014

  • Yamamura, Masaki; Albrecht, Marcel; Albrecht, Markus
  • Inorganic Chemistry, Vol. 53, Issue 3
  • DOI: 10.1021/ic402116j

WinGX and ORTEP for Windows : an update
journal, July 2012


Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination
journal, January 2015

  • Krause, Lennard; Herbst-Irmer, Regine; Sheldrick, George M.
  • Journal of Applied Crystallography, Vol. 48, Issue 1
  • DOI: 10.1107/S1600576714022985

Ligand Noninnocence in Silver Corroles: A XANES Investigation: Ligand Noninnocence in Silver Corroles: A XANES Investigation
journal, June 2016

  • Sarangi, Ritimukta; Giles, Logan J.; Thomas, Kolle E.
  • European Journal of Inorganic Chemistry, Vol. 2016, Issue 20
  • DOI: 10.1002/ejic.201600413

Aluminium complexes of N2O2-type dipyrrins: the first hetero-multinuclear complexes of metallo-dipyrrins with high fluorescence quantum yields
journal, January 2009

  • Ikeda, Chusaku; Ueda, Satoko; Nabeshima, Tatsuya
  • Chemical Communications, Issue 18
  • DOI: 10.1039/b820141b

Oxidations Catalyzed by Metallocorroles
journal, February 2004

  • Gross, Zeev; Gray, Harry B.
  • Advanced Synthesis & Catalysis, Vol. 346, Issue 23
  • DOI: 10.1002/adsc.200303145

Structural, electrochemical and spectroelectrochemical study on the geometric and electronic structures of [(corrolato)Au III ] n (n = 0, +1, −1) complexes
journal, January 2016

  • Sinha, Woormileela; Sommer, Michael G.; van der Meer, Margarethe
  • Dalton Transactions, Vol. 45, Issue 7
  • DOI: 10.1039/C5DT03737A

Gold corroles
journal, February 2011

  • Alemayehu, Abraham B.; Ghosh, Abhik
  • Journal of Porphyrins and Phthalocyanines, Vol. 15, Issue 02
  • DOI: 10.1142/S1088424611003045

Co(III) complexes of tetradentate X3L type ligands: Synthesis, electronic structure, and reactivity
journal, May 2015


Molecular structure of gold 2,3,7,8,12,13,17,18-octabromo-5,10,15-tris(4′-pentafluorosulfanylphenyl)corrole: Potential insights into the insolubility of gold octabromocorroles
journal, July 2018

  • Thomas, Kolle E.; Gagnon, Kevin J.; MCormick, Laura J.
  • Journal of Porphyrins and Phthalocyanines, Vol. 22, Issue 07
  • DOI: 10.1142/S1088424618500815

Seven Clues to Ligand Noninnocence: The Metallocorrole Paradigm
journal, March 2019


Chemistry with ADF
journal, January 2001

  • te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
  • DOI: 10.1002/jcc.1056

Palladium-Catalyzed Cross-Coupling of Pyrrole Anions with Aryl Chlorides, Bromides, and Iodides
journal, October 2004

  • Rieth, Ryan D.; Mankad, Neal P.; Calimano, Elisa
  • Organic Letters, Vol. 6, Issue 22
  • DOI: 10.1021/ol048367m

Gold Tris(carboxyphenyl)corroles as Multifunctional Materials: Room Temperature Near-IR Phosphorescence and Applications to Photodynamic Therapy and Dye-Sensitized Solar Cells
journal, July 2016

  • Alemayehu, Abraham B.; Day, Nicholas U.; Mani, Tomoyasu
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 29
  • DOI: 10.1021/acsami.6b04269

Revisiting the Electronic Ground State of Copper Corroles
journal, January 2007

  • Bröring, Martin; Brégier, Frédérique; Cónsul Tejero, Esther
  • Angewandte Chemie International Edition, Vol. 46, Issue 3
  • DOI: 10.1002/anie.200603676

Electronic Structure of Gallium, Copper, and Nickel Complexes of Corrole. High-Valent Transition Metal Centers versus Noninnocent Ligands
journal, May 2000

  • Ghosh, Abhik; Wondimagegn, Tebikie; Parusel, Andreas B. J.
  • Journal of the American Chemical Society, Vol. 122, Issue 21
  • DOI: 10.1021/ja9943243

Ligand Noninnocence in Cobalt Dipyrrin–Bisphenols: Spectroscopic, Electrochemical, and Theoretical Insights Indicating an Emerging Analogy with Corroles
journal, January 2019


Dipyrrinphenol–Mn(iii) complex: synthesis, electrochemistry, spectroscopic characterisation and reactivity
journal, January 2011

  • El Ghachtouli, Sanae; Wójcik, Karolina; Copey, Laurent
  • Dalton Transactions, Vol. 40, Issue 36
  • DOI: 10.1039/c1dt10868a

Cobalt- and Rhodium-Corrole-Triphenylphosphine Complexes Revisited: The Question of a Noninnocent Corrole
journal, December 2017


Ligand-Centered Redox Activity in Cobalt(II) and Nickel(II) Bis(phenolate)-Dipyrrin Complexes
journal, October 2012

  • Kochem, Amélie; Chiang, Linus; Baptiste, Benoit
  • Chemistry - A European Journal, Vol. 18, Issue 46
  • DOI: 10.1002/chem.201202882

ShelXle : a Qt graphical user interface for SHELXL
journal, November 2011

  • Hübschle, Christian B.; Sheldrick, George M.; Dittrich, Birger
  • Journal of Applied Crystallography, Vol. 44, Issue 6
  • DOI: 10.1107/S0021889811043202

Synthesis and Molecular Structure of Gold Triarylcorroles
journal, December 2011

  • Thomas, Kolle E.; Alemayehu, Abraham B.; Conradie, Jeanet
  • Inorganic Chemistry, Vol. 50, Issue 24
  • DOI: 10.1021/ic202023r

Valence ionization potentials and cation radicals of prototype porphyrins. The remarkable performance of nonlocal density functional theory
journal, October 1997

  • Ghosh, Abhik; Vangberg, Torgil
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 97, Issue 1-4
  • DOI: 10.1007/s002140050247

SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370

Halterman Corroles and Their Use as a Probe of the Conformational Dynamics of the Inherently Chiral Copper Corrole Chromophore
journal, March 2018


Geometry optimizations in the zero order regular approximation for relativistic effects
journal, May 1999

  • van Lenthe, Erik; Ehlers, Andreas; Baerends, Evert-Jan
  • The Journal of Chemical Physics, Vol. 110, Issue 18
  • DOI: 10.1063/1.478813

First-Principles Quantum Chemical Studies of Porphyrins
journal, April 1998

  • Ghosh, Abhik
  • Accounts of Chemical Research, Vol. 31, Issue 4
  • DOI: 10.1021/ar950033x

X-ray Structure and Variable Temperature NMR Spectra of [ m eso -Triarylcorrolato]copper(III)
journal, July 2003

  • Brückner, Christian; Briñas, Raymond P.; Krause Bauer, Jeanette A.
  • Inorganic Chemistry, Vol. 42, Issue 15
  • DOI: 10.1021/ic034080u

Synthesis and Molecular Structure of a Copper Octaiodocorrole
journal, May 2018


The ultraviolet photoelectron spectrum of free-base porphyrin revisited. The performance of local density functional theory
journal, October 1993


DFT at Its Best: Metal- versus Ligand-Centered Reduction in Nickel Hydroporphyrins
journal, November 2008

  • Ryeng, Hege; Gonzalez, Emmanuel; Ghosh, Abhik
  • The Journal of Physical Chemistry B, Vol. 112, Issue 47
  • DOI: 10.1021/jp805486b

Copper β-Octakis(trifluoromethyl)corroles: New Paradigms for Ligand Substituent Effects in Transition Metal Complexes
journal, November 2008

  • Thomas, Kolle Ekaney; Wasbotten, Ingar H.; Ghosh, Abhik
  • Inorganic Chemistry, Vol. 47, Issue 22
  • DOI: 10.1021/ic801101k

Demetalation of copper undecaarylcorroles: Molecular structures of a free-base undecaarylisocorrole and a gold undecaarylcorrole
journal, September 2016


Electronic Structure of Cobalt–Corrole–Pyridine Complexes: Noninnocent Five-Coordinate Co(II) Corrole–Radical States
journal, December 2017

  • Ganguly, Sumit; Conradie, Jeanet; Bendix, Jesper
  • The Journal of Physical Chemistry A, Vol. 121, Issue 50
  • DOI: 10.1021/acs.jpca.7b09440

Synthesis of a new family of ionophores based on aluminum–dipyrrin complexes (ALDIPYs) and their strong recognition of alkaline earth ions
journal, January 2016

  • Saikawa, Makoto; Daicho, Manami; Nakamura, Takashi
  • Chemical Communications, Vol. 52, Issue 21
  • DOI: 10.1039/C6CC00250A

Efficient luminescent properties and cation recognition ability of heavy group 13 element complexes of N 2 O 2 - and N 2 O 4 -type dipyrrins
journal, January 2019

  • Sumiyoshi, Akinobu; Chiba, Yusuke; Matsuoka, Ryota
  • Dalton Transactions, Vol. 48, Issue 35
  • DOI: 10.1039/C9DT02403D

Electronic Structure and Reactivity of One-Electron-Oxidized Copper(II) Bis(phenolate)–Dipyrrin Complexes
journal, April 2018


Facile Estimation of Catalytic Activity and Selectivities in Copolymerization of Propylene Oxide with Carbon Dioxide Mediated by Metal Complexes with Planar Tetradentate Ligand
journal, July 2014

  • Ohkawara, Takahiro; Suzuki, Kohei; Nakano, Koji
  • Journal of the American Chemical Society, Vol. 136, Issue 30
  • DOI: 10.1021/ja5046814

Gold(I) and Gold(III) Corroles
journal, October 2011

  • Rabinovich, Elena; Goldberg, Israel; Gross, Zeev
  • Chemistry - A European Journal, Vol. 17, Issue 44
  • DOI: 10.1002/chem.201102348

Effect of Selective CF 3 Substitution on the Physical and Chemical Properties of Gold Corroles
journal, July 2017

  • Sudhakar, Kolanu; Mizrahi, Amir; Kosa, Monica
  • Angewandte Chemie International Edition, Vol. 56, Issue 33
  • DOI: 10.1002/anie.201705007

X-ray Absorption Spectroscopy as a Probe of Ligand Noninnocence in Metallocorroles: The Case of Copper Corroles
journal, May 2019


Molecular structure of a gold β-octakis(trifluoromethyl)- meso -triarylcorrole: an 85° difference in saddling dihedral relative to copper
journal, April 2012


The Structural Chemistry of Metallocorroles: Combined X-ray Crystallography and Quantum Chemistry Studies Afford Unique Insights
journal, March 2012

  • Thomas, Kolle E.; Alemayehu, Abraham B.; Conradie, Jeanet
  • Accounts of Chemical Research, Vol. 45, Issue 8
  • DOI: 10.1021/ar200292d

Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

Mono-DMSO ligated cobalt nitrophenylcorroles: electrochemical and spectral characterization
journal, January 2018

  • Jiang, X.; Shan, W.; Desbois, N.
  • New Journal of Chemistry, Vol. 42, Issue 10
  • DOI: 10.1039/C8NJ00300A

Metallocorroles as Nonprecious-Metal Catalysts for Oxygen Reduction
journal, October 2015

  • Levy, Naomi; Mahammed, Atif; Kosa, Monica
  • Angewandte Chemie International Edition, Vol. 54, Issue 47
  • DOI: 10.1002/anie.201505236

Substituent Effects on Valence Ionization Potentials of Free Base Porphyrins: A Local Density Functional Study
journal, April 1995

  • Ghosh, Abhik
  • Journal of the American Chemical Society, Vol. 117, Issue 16
  • DOI: 10.1021/ja00121a025

Manganese(III) Complexes of Bis(hydroxyphenyl)dipyrromethenes Are Potent Orally Active Peroxynitrite Scavengers
journal, March 2011

  • Rausaria, Smita; Kamadulski, Andrew; Rath, Nigam P.
  • Journal of the American Chemical Society, Vol. 133, Issue 12
  • DOI: 10.1021/ja110427e

Monomeric and dimeric red/NIR-fluorescent dipyrrin–germanium complexes: facile monomer–dimer interconversion driven by acid/base additions
journal, December 2013


Undecaphenylcorroles
journal, September 2012

  • Berg, Steffen; Thomas, Kolle E.; Beavers, Christine M.
  • Inorganic Chemistry, Vol. 51, Issue 18
  • DOI: 10.1021/ic301388e

Left-right correlation energy
journal, March 2001


Relativistic regular two‐component Hamiltonians
journal, September 1993

  • Lenthe, E. van; Baerends, E. J.; Snijders, J. G.
  • The Journal of Chemical Physics, Vol. 99, Issue 6
  • DOI: 10.1063/1.466059

Nonplanar, Noninnocent, and Chiral: A Strongly Saddled Metallocorrole
journal, September 2010

  • Alemayehu, Abraham B.; Hansen, Lars Kristian; Ghosh, Abhik
  • Inorganic Chemistry, Vol. 49, Issue 17
  • DOI: 10.1021/ic1008736

Ligand Noninnocence in Coinage Metal Corroles: A Silver Knife-Edge
journal, September 2015

  • Thomas, Kolle E.; Vazquez-Lima, Hugo; Fang, Yuanyuan
  • Chemistry - A European Journal, Vol. 21, Issue 47
  • DOI: 10.1002/chem.201502150

Relativistic total energy using regular approximations
journal, December 1994

  • van Lenthe, E.; Baerends, E. J.; Snijders, J. G.
  • The Journal of Chemical Physics, Vol. 101, Issue 11
  • DOI: 10.1063/1.467943

High-valent transition metal centers and noninnocent ligands in metalloporphyrins and related molecules: a broad overview based on quantum chemical calculations
journal, September 2001

  • Ghosh, Abhik; Steene, Erik
  • JBIC Journal of Biological Inorganic Chemistry, Vol. 6, Issue 7
  • DOI: 10.1007/s007750100275

Corrections to tabulated anomalous-scattering factors
journal, March 1990

  • Kissel, L.; Pratt, R. H.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 46, Issue 3
  • DOI: 10.1107/S0108767389010718

Copper Corroles Are Inherently Saddled
journal, August 2009

  • Alemayehu, Abraham B.; Gonzalez, Emmanuel; Hansen, Lars Kristian
  • Inorganic Chemistry, Vol. 48, Issue 16
  • DOI: 10.1021/ic900744v

A Metallocorrole with Orthogonal Pyrrole Rings
journal, March 2011

  • Thomas, Kolle E.; Conradie, Jeanet; Hansen, Lars K.
  • European Journal of Inorganic Chemistry, Vol. 2011, Issue 12
  • DOI: 10.1002/ejic.201100170