Topological And Steric Constraints To Stabilize Heteroleptic Copper(I) Complexes Combining Phenanthroline Ligands And Phosphines.
Michel Holler, Béatrice Delavaux-Nicot, Jean-François Nierengarten
Published 2019 · Medicine, Chemistry
Download PDFAnalyze on Scholarcy
Heteroleptic copper(I) complexes combining phenanthroline derivatives (NN) and chelating bisphosphine ligands (PP) are an important class of luminescent materials for various applications. Although thermodynamically stable, [Cu(NN)(PP)]+ derivatives are also kinetically unstable. As a result, a dynamic ligand-exchange reaction is often observed in solution, leading to a dynamic mixture of heteroleptic and homoleptic complexes. To prevent the formation of the homoleptic species, macrocyclic phenanthroline ligands have been used for the preparation of [Cu(NN)(PP)]+ pseudorotaxanes. The topological constraint resulting from the macrocyclic structure of the NN ligand drives the thermodynamic equilibrium towards the exclusive formation of the heteroleptic complex as long as the macrocycle is large and flexible enough to allow for the threading of the PP ligand. Conversely, when the threading is prevented by steric constraints, unprecedented copper(I) complexes with a trigonal coordination geometry are obtained. These results are summarized in the present concept article.
This paper references
Ultrafast excited-state dynamics of copper(I) complexes.
Munetaka Iwamura (2015)
Improvement of the photochemical reactivity of [Cu(dmp)P2]+ (dmp=2,9-dimethyl-1,10-phenanthroline; P=tertiary phosphine) by substituting PPh3 with larger phosphines: application to photoreduction of methylviologen
Shigeyoshi Sakaki (1987)
Successful photocatalytic reduction of methylviologen (MV2+) with [Cu(NN)(PPh3)2]+ (NN = 2,9-dimethyl-1,10-phenanthroline or 4,4',6,6'-tetramethyl-2,2'-bipyridine) upon near-UV-light irradiation and a novel solvent effect on its catalytic activity
Shigeyoshi Sakaki (1986)
Photophysical properties of three coordinated copper(i) complexes bearing 1,10-phenanthroline and a monodentate phosphine ligand.
Daichi Kakizoe (2017)
Phosphorescent Cu(I) complexes of 2-(2'-pyridylbenzimidazolyl)benzene: impact of phosphine ancillary ligands on electronic and photophysical properties of the Cu(I) complexes.
T. McCormick (2006)
Heteroleptic diimine copper(I) complexes with large extinction coefficients: synthesis, quantum chemistry calculations and physico-chemical properties.
Martina Sandroni (2013)
Dynamic topomerization of Cu(I)-complexed pseudorotaxanes.
Meera Mohankumar (2013)
Templated synthesis of interlocked macrocyclic ligands, the catenands. Preparation and characterization of the prototypical bis-30 membered ring system
Christiane Dietrich-Buchecker (1990)
Elucidating the Nature of the Excited State of a Heteroleptic Copper Photosensitizer by using Time-Resolved X-ray Absorption Spectroscopy.
D. Moonshiram (2018)
Visible-Light-Driven Photosystems Using Heteroleptic Cu(I) Photosensitizers and Rh(III) Catalysts To Produce H2.
Bradley J. McCullough (2018)
Preparation of copper(I) pseudo-rotaxanes from bis-phosphine ligands.
Meera Mohankumar (2012)
Heteroleptic copper(I) complexes prepared from phenanthroline and bis-phosphine ligands.
Adrien Kaeser (2013)
Thermally activated delayed fluorescence (TADF) and enhancing photoluminescence quantum yields of [Cu(I)(diimine)(diphosphine)](+) complexes-photophysical, structural, and computational studies.
Charlotte L Linfoot (2014)
Temperature- and voltage-induced ligand rearrangement of a dynamic electroluminescent metallopolymer.
Demet Asil (2014)
Photochemistry and Photophysics of Coordination Compounds: Copper
N. Armaroli (2007)
Photocatalytic water reduction with copper-based photosensitizers: a noble-metal-free system.
Shu-Ping Luo (2013)
Designing Highly Efficient CuI Photosensitizers for Photocatalytic H2 Evolution from Water.
Jae‐kwan Kim (2017)
Stable mixed phenanthroline copper(i) complexes. Key building blocks for supramolecular coordination chemistry
Michael Schmittel (1997)
CF3 Substitution of [Cu(P^P)(bpy)][PF6 ] Complexes: Effects on Photophysical Properties and Light-Emitting Electrochemical Cell Performance.
S. Keller (2018)
Metal-coordination-driven dynamic heteroleptic architectures.
Soumen Das De (2010)
Homoleptic Copper(I), Silver(I), and Gold(I) Bisphosphine Complexes
Adrien Kaeser (2014)
Highly Efficient Green Phosphorescent Organic Light-Emitting Diodes Based on CuI Complexes†
Qisheng Zhang (2004)
Long-lived excited states of zwitterionic copper(I) complexes for photoinduced cross-dehydrogenative coupling reactions.
Bin Wang (2015)
Structures and photophysical properties of copper(I) complexes bearing diphenylphenanthroline and bis(diphenylphosphino)alkane: the effect of phenyl groups on the phenanthroline ligand.
Taro Tsubomura (2015)
Substituent effects and the photoluminescence of Cu(PPh3)2(NN)+ systems
Alan A. Del Paggio (1983)
Light harvesting with Earth abundant d-block metals: Development of sensitizers in dye-sensitized solar cells (DSCs)
Biljana Bozic-Weber (2013)
Solvated-ion-pairing-sensitive molecular bistability based on copper(I)-coordinated pyrimidine ring rotation.
Michihiro Nishikawa (2013)
Synthesis and structural characterization of Cu(I) and Ni(II) complexes that contain the bis[2-(diphenylphosphino)phenyl]ether ligand. Novel emission properties for the Cu(I) species.
Shan-Ming Kuang (2002)
Solid-State and Solution Structural Properties of Copper(I) Compounds with Bidentate Phosphane Ligands
P. Comba (1999)
Blue and orange oxygen responsive emissions in the solid state based on copper(I) complexes bearing dodecafluorinated diphosphine and 1,10-phenanthroline derivative ligands
Masaya Washimi (2017)
Outstanding luminescence from neutral copper(I) complexes with pyridyl-tetrazolate and phosphine ligands.
Larissa Bergmann (2013)
Regulation of the rate of dinucleation of a monocopper(I) complex containing bipyrimidine rotary units by restricted double pyrimidine rotation.
Yohei Hattori (2014)
A Highly Emissive Heteroleptic Copper(I) Bis(phenanthroline) Complex: [Cu(dbp)(dmp)]+ (dbp = 2,9-Di-tert-butyl-1,10-phenanthroline; dmp = 2,9-Dimethyl-1,10-phenanthroline)
Mark T. Miller (1999)
Ring-in-ring structures from phenanthroline macrocycles with exo- and endotopic binding sites.
Michael Schmittel (2002)
Heteroleptic Cu(I) complexes containing phenanthroline-type and 1,1′-bis(diphenylphosphino)ferrocene ligands: Structure and electronic properties
Nicola Armaroli (2007)
Advances in the light conversion properties of Cu(I)-based photosensitizers
Megan S. Lazorski (2014)
Shine bright or live long: substituent effects in [Cu(N^N)(P^P)]+-based light-emitting electrochemical cells where N^N is a 6-substituted 2,2′-bipyridine
S. Keller (2016)
Copper(I) complexes for sustainable light-emitting electrochemical cells
Ruben Monteiro da Costa (2011)
Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands: Rationalization of the Photophysical and Electrochemical Properties.
Enrico Leoni (2018)
Metal-directed self-assembly of two- and three-dimensional synthetic receptors
Makoto Fujita (1998)
Dual emissions from (2,9-dimethyl-1,10-phenanthroline)bis(tertiary phosphine)copper(1+) systems in a rigid glass: influence of the phosphine donor strength
D. Casadonte (1987)
Electrophosphorescent homo- and heteroleptic copper(I) complexes prepared from various bis-phosphine ligands.
Omar Moudam (2007)
Heteroleptic diimine–diphosphine Cu(I) complexes as an alternative towards noble-metal based photosensitizers: Design strategies, photophysical properties and perspective applications
Y. Zhang (2018)
Heteroleptic Copper Photosensitizers: Why an Extended π-System Does Not Automatically Lead to Enhanced Hydrogen Production.
Martin Heberle (2017)
Combining topological and steric constraints for the preparation of heteroleptic copper(I) complexes.
Meera Mohankumar (2014)
Peripheral halo-functionalization in [Cu(N^N)(P^P)]+ emitters: influence on the performances of light-emitting electrochemical cells.
Fabian Brunner (2016)
Earth-abundant photocatalytic systems for the visible-light-driven reduction of CO2 to CO
Alonso Rosas-Hernández (2017)
Photocatalytic Hydrogen Production with Copper Photosensitizer–Titanium Dioxide Composites
Michael Karnahl (2014)
The topomer-sampling model of protein folding.
Derek A. Debe (1999)
Synthesis and self-assembly of a rigid exotopic bisphenanthroline macrocycle: surface patterning and a supramolecular nanobasket.
Venkateshwarlu Kalsani (2004)
Improving the photophysical properties of copper(I) bis(phenanthroline) complexes
Aurélie Lavie-Cambot (2008)
Blue-light emission of Cu(I) complexes and singlet harvesting.
Rafał Czerwieniec (2011)
A series of luminescent Cu(I) mixed-ligand complexes containing 2,9-dimethyl-1,10-phenanthroline and simple diphosphine ligands.
K. Saito (2006)
Highly Efficient Electroluminescence from Green‐Light‐Emitting Electrochemical Cells Based on CuI Complexes
Qisheng Zhang (2006)
The emergence of copper(I)-based dye sensitized solar cells.
Catherine E Housecroft (2015)
"Let's twist again"--double-stranded, triple-stranded, and circular helicates.
M. Albrecht (2001)
Highly emissive copper(I) complexes bearing diimine and bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane.
Michihiro Nishikawa (2015)
Supramolecular coordination: self-assembly of finite two- and three-dimensional ensembles.
Rajesh Chakrabarty (2011)
Shining Light on Copper: Unique Opportunities for Visible-Light-Catalyzed Atom Transfer Radical Addition Reactions and Related Processes.
Oliver Reiser (2016)
Photoswitching of Copper(I) Chromophores with Dithienylethene-Based Ligands.
Zhen Xu (2018)
Syntheses, Photoluminescence, and Electroluminescence of a Series of Sublimable Bipolar Cationic Cuprous Complexes with Thermally Activated Delayed Fluorescence.
F. Zhang (2017)
Diversity of copper(I) complexes showing thermally activated delayed fluorescence: basic photophysical analysis.
Rafał Czerwieniec (2015)
Neutral Mononuclear Copper(I) Complexes: Synthesis, Crystal Structures, and Photophysical Properties.
Yinghui Sun (2016)
Stimuli-responsive pyrimidine ring rotation in copper complexes for switching their physical properties.
Michihiro Nishikawa (2013)
Bright coppertunities: multinuclear Cu(I) complexes with N-P ligands and their applications.
Manuela Wallesch (2014)
Copper-Based Photosensitisers in Water Reduction: A More Efficient In Situ Formed System and Improved Mechanistic Understanding.
A. Lennox (2016)
Une nouvelle famille de molecules : les metallo-catenanes
C. Dietrich-Buchecker (1983)
Substituted [Cu(I)(POP)(bipyridyl)] and related complexes: synthesis, structure, properties and applications to dye-sensitised solar cells.
Charlotte L Linfoot (2010)
Copper(I) complexes of bis(2-(diphenylphosphino)phenyl) ether: synthesis, reactivity, and theoretical calculations.
Ramalingam Venkateswaran (2007)
Solution study of 2-catenates: increase of stability constants by interlocking coordinating subunits
Françoise Arnaud-Neu (1988)
Heteroleptic Cu-Based Sensitizers in Photoredox Catalysis.
Augusto C. Hernandez-Perez (2016)
Recent advances in organic light-emitting devices comprising copper complexes: A realistic approach for low-cost and highly emissive devices?
Frédéric Dumur (2015)
Heteroleptic bis-diimine copper(I) complexes for applications in solar energy conversion
M. Sandroni (2016)
Simple Cu(I) complexes with unprecedented excited-state lifetimes.
D. G. Cuttell (2002)
Geometry changes of a Cu(I) phenanthroline complex on photoexcitation in a confining medium by time-resolved X-ray diffraction.
Philip Coppens (2004)
Quantitative formation and clean metal exchange processes of large void (>5000 Å3) nanobox structures
Michael Schmittel (2002)
Substitution-controlled excited state processes in heteroleptic copper(I) photosensitizers used in hydrogen evolving systems.
Stefanie Tschierlei (2014)
Interplays of excited state structures and dynamics in copper(I) diimine complexes: Implications and perspectives
Michael W Mara (2015)
Phosphorescent properties of metal-free diphosphine ligands and effects of copper binding.
Junpei Yuasa (2013)
383. The oxidation–reduction potentials of some copper complexes
B. James (1961)
Photostudies of 2,2'-bipyridine bis(triphenylphosphine)copper(1+), 1,10-phenanthroline bis(triphenylphosphine)copper(1+), and 2,9-dimethyl-1,10-phenanthroline bis(triphenylphosphine)copper(1+) in solution and in rigid, low-temperature glasses. Simultaneous multiple emissions from intraligand and cha
Rosemary A. Rader (1981)
Self-recognition in helicate self-assembly: spontaneous formation of helical metal complexes from mixtures of ligands and metal ions.
R. Kramer (1993)
Highly efficient thermally activated fluorescence of a new rigid Cu(I) complex [Cu(dmp)(phanephos)]+.
Rafał Czerwieniec (2013)
Direct observation of intersystem crossing in a thermally activated delayed fluorescence copper complex in the solid state
Larissa Bergmann (2016)
[Cu(bpy)(P^P)]⁺ containing light-emitting electrochemical cells: improving performance through simple substitution.
Sarah Keller (2014)
Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes.
Meera Mohankumar (2018)
Atom‐Transfer Radical Addition Photocatalysis Using a Heteroleptic Copper Complex
Kazuki Matsuo (2018)
Efficient Color-Tunable Copper(I) Complexes and Their Applications in Solution-Processed Organic Light-Emitting Diodes.
Gary Kwok-Ming So (2017)
Highly Luminescent CuI Complexes for Light-Emitting Electrochemical Cells†
N. Armaroli (2006)
Heteroleptic copper(I) complexes coupled with methanofullerene: synthesis, electrochemistry, and photophysics.
Andrea Listorti (2008)
This paper is referenced by
Homoleptic versus heteroleptic trinuclear systems with mixed l-cysteinate and d-penicillaminate regulated by a diphosphine linker.
Sasikarn Hanprasit (2020)
Copper(I) Phosphinooxazoline Complexes: Impact of the Ligand Substitution and Steric Demand on the Electrochemical and Photophysical Properties
Robin Giereth (2019)
Dinuclear Copper Complexes Triply Bridged by a Tetraphosphane, rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2: Dinuclear Copper Complexes Triply Bridged by a Tetraphosphane, rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2
Tomoaki Tanase (2019)
Dinuclear Copper(I) Complexes Combining Bis(diphenylphosphanyl)acetylene with 1,10-Phenanthroline Ligands: Dinuclear Copper(I) Complexes Combining Bis(diphenylphosphanyl)acetylene with 1,10-Phenanthroline Ligands
Jean-François Nierengarten (2019)
Design and application of diimine-based copper(i) complexes in photoredox catalysis.
Tamas Foeldesi (2019)