Advances in the light conversion properties of Cu(I)-based photosensitizers

Abstract The need to develop low-cost, sustainable, earth abundant fuel sources is becoming paramount as the rate of global energy consumption continues to increase. Toward this goal, solar energy conversion is an obvious choice, yet the current molecular based technologies still rely heavily on expensive, non-earth abundant photosensitizers, which limits the net benefits of these systems. Complexes of copper(I) have been recognized for decades as viable low-cost, earth abundant alternative photosensitizers in solar energy conversion technologies; however, when used in solution based applications, issues such as geometrical distortions associated with photoexcitation and ligand lability has frustrated numerous research efforts. Fortunately, these investigations have not been in vain, and many investigations have successfully circumvented the aforementioned issues. Recent reports on Cu(I) based photosensitizers demonstrate that they are beginning to rival the performance metrics of the more costly, less earth abundant species typically used in solution-based solar energy conversion schemes. Therefore, this minireview focuses on the most recent and influential advances made in the field of Cu(I) based photosensitizers.

[1]  Vincenzo Balzani,et al.  Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence , 1988 .

[2]  A. Talarico,et al.  Photoinduced electron transfer in multiporphyrinic interlocked structures: the effect of copper(I) coordination in the central site. , 2004, Chemistry.

[3]  Koichi Nozaki,et al.  Structure-dependent photophysical properties of singlet and triplet metal-to-ligand charge transfer states in copper(I) bis(diimine) compounds. , 2003, Inorganic chemistry.

[4]  Felix N. Castellano,et al.  Photon upconversion based on sensitized triplet-triplet annihilation , 2010 .

[5]  R. Colton,et al.  Copper(I) tetrahydroborate derivatives containing phosphine and phenanthroline ligands : an electrospray mass spectrometric study of species in solution , 1993 .

[6]  E. Blart,et al.  Heteroleptic diimine copper(I) complexes with large extinction coefficients: synthesis, quantum chemistry calculations and physico-chemical properties. , 2013, Dalton transactions.

[7]  Alex C. Bissember,et al.  Transition-metal-catalyzed alkylations of amines with alkyl halides: photoinduced, copper-catalyzed couplings of carbazoles. , 2013, Angewandte Chemie.

[8]  Jillian L Dempsey,et al.  Long-lived and efficient emission from mononuclear amidophosphine complexes of copper. , 2007, Inorganic chemistry.

[9]  Gianluca Accorsi,et al.  Electrophosphorescent homo- and heteroleptic copper(I) complexes prepared from various bis-phosphine ligands. , 2007, Chemical communications.

[10]  F. Castellano,et al.  Orange-to-blue and red-to-green photon upconversion with a broadband absorbing copper(I) MLCT sensitizer. , 2013, Chemical communications.

[11]  Jean-Pierre Sauvage,et al.  Interlocked macrocyclic ligands: a kinetic catenand effect in copper(I) complexes , 1985 .

[12]  N. Tkachenko,et al.  Probing the excited state dynamics of a new family of Cu(I)-complexes with an enhanced light absorption capacity: excitation-wavelength dependent population of states through branching. , 2013, Physical chemistry chemical physics : PCCP.

[13]  Hartmut Yersin,et al.  Singlet harvesting with brightly emitting Cu(I) and metal-free organic compounds , 2012, Photonics Europe.

[14]  Martin Nieger,et al.  Copper(I) complexes based on five-membered P^N heterocycles: structural diversity linked to exciting luminescence properties. , 2013, Inorganic chemistry.

[15]  M. Rehahn,et al.  First synthesis of soluble, well defined coordination polymers from kinetically unstable copper(I) complexes , 1996 .

[16]  M. Neuburger,et al.  An element of surprise--efficient copper-functionalized dye-sensitized solar cells. , 2008, Chemical communications.

[17]  J. Burstyn,et al.  Facile oxidation-based synthesis of sterically encumbered four-coordinate bis(2,9-di-tert-butyl-1,10-phenanthroline)copper(I) and related three-coordinate copper(I) complexes. , 2007, Inorganic chemistry.

[18]  Keita Sekizawa,et al.  Temperature-dependent Emission of Copper(I) Phenanthroline Complexes with Bulky Substituents: Estimation of an Energy Gap between the Singlet and Triplet MLCT States , 2010 .

[19]  Daniel M. Zink,et al.  Heteroleptic, Dinuclear Copper(I) Complexes for Application in Organic Light-Emitting Diodes , 2013 .

[20]  C. M. Elliott,et al.  Dye-Sensitized Solar Cell Studies of a Donor-Appended Bis(2,9-dimethyl-1,10-phenanthroline) Cu(I) Dye Paired with a Cobalt-Based Mediator , 2013 .

[21]  D. McMillin,et al.  Competitive energy-transfer and reductive quenching of the CT excited states of copper(l) phenanthrolines , 1996 .

[22]  Ai-Min Ren,et al.  Theoretical study on photophysical property of cuprous bis-phenanthroline coordination complexes , 2012 .

[23]  E. Blart,et al.  Structures and spectral properties of heteroleptic copper (I) complexes: A theoretical study based on density functional theory , 2012 .

[24]  Masashi Hashimoto,et al.  Application of neutral d10 coinage metal complexes with an anionic bidentate ligand in delayed fluorescence-type organic light-emitting diodes , 2013 .

[25]  Hartmut Yersin,et al.  Brightly blue and green emitting Cu(I) dimers for singlet harvesting in OLEDs. , 2013, The journal of physical chemistry. A.

[26]  P. Gantzel,et al.  Effects of Sterics and Electronic Delocalization on the Photophysical, Structural, and Electrochemical Properties of 2,9-Disubstituted 1,10-Phenanthroline Copper(I) Complexes. , 1999, Inorganic chemistry.

[27]  Thomas J. Meyer,et al.  Photochemistry of tris(2,2'-bipyridine)ruthenium(2+) ion (Ru(bpy)32+). Solvent effects , 1983 .

[28]  F. Castellano,et al.  Design of a long-lifetime, earth-abundant, aqueous compatible Cu(I) photosensitizer using cooperative steric effects. , 2013, Inorganic chemistry.

[29]  J. Zink,et al.  Influence of ligand substitution on excited state structural dynamics in Cu(I) bisphenanthroline complexes. , 2010, The journal of physical chemistry. B.

[30]  F. Castellano,et al.  Photochemical upconversion approach to broad-band visible light generation. , 2008, The journal of physical chemistry. A.

[31]  M. Beller,et al.  Photocatalytic Hydrogen Production with Copper Photosensitizer–Titanium Dioxide Composites , 2014 .

[32]  Qing Wang,et al.  DFT-INDO/S modeling of new high molar extinction coefficient charge-transfer sensitizers for solar cell applications. , 2006, Inorganic chemistry.

[33]  J. Peters,et al.  Amido-bridged Cu2N2 diamond cores that minimize structural reorganization and facilitate reversible redox behavior between a Cu1Cu1 and a class III delocalized Cu1.5Cu1.5 species. , 2004, Journal of the American Chemical Society.

[34]  J. Peters,et al.  Efficient luminescence from easily prepared three-coordinate copper(I) arylamidophosphines. , 2010, Chemical communications.

[35]  H. Nishihara,et al.  Stimuli-responsive pyrimidine ring rotation in copper complexes for switching their physical properties. , 2013, Physical chemistry chemical physics : PCCP.

[36]  D. McMillin,et al.  Reinvestigation of the absorbing and emitting charge-transfer excited states of [Cu(NN)2]+ systems , 1991 .

[37]  M. Schmittel,et al.  New Sterically Encumbered 2,9‐Diarylphenanthrolines for the Selective Formation of Heteroleptic Bis(phenanthroline)copper(I) Complexes , 2001 .

[38]  H. Nishihara,et al.  Reversible copper(II)/(I) electrochemical potential switching driven by visible light-induced coordinated ring rotation. , 2012, Journal of the American Chemical Society.

[39]  Nosheen A. Gothard,et al.  Strong steric hindrance effect on excited state structural dynamics of Cu(I) diimine complexes. , 2012, The journal of physical chemistry. A.

[40]  D. McMillin,et al.  The basis of aryl substituent effects on charge-transfer absorption intensities , 1986 .

[41]  G. B. Shaw,et al.  Ultrafast structural rearrangements in the MLCT excited state for copper(I) bis-phenanthrolines in solution. , 2006, Journal of the American Chemical Society.

[42]  D. Gosztola,et al.  Rapid excited-state structural reorganization captured by pulsed X-rays. , 2002, Journal of the American Chemical Society.

[43]  Guy Jennings,et al.  MLCT state structure and dynamics of a copper(I) diimine complex characterized by pump-probe X-ray and laser spectroscopies and DFT calculations. , 2003, Journal of the American Chemical Society.

[44]  R. Thummel,et al.  Crowded Cu(I) complexes involving benzo[h]quinoline: pi-stacking effects and long-lives excited states. , 2001, Inorganic chemistry.

[45]  F. Lytle,et al.  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 , 1981 .

[46]  Alex C. Bissember,et al.  A versatile approach to Ullmann C-N couplings at room temperature: new families of nucleophiles and electrophiles for photoinduced, copper-catalyzed processes. , 2013, Journal of the American Chemical Society.

[47]  Jean-Pierre Sauvage,et al.  Interlocking of molecular threads: from the statistical approach to the templated synthesis of catenands , 1987 .

[48]  F. Castellano Transition metal complexes meet the rylenes. , 2012, Dalton transactions.

[49]  D. McMillin,et al.  Steric Effects in the Ground and Excited States of Cu(NN)2+ Systems , 1997 .

[50]  G. C. Fu,et al.  A new family of nucleophiles for photoinduced, copper-catalyzed cross-couplings via single-electron transfer: reactions of thiols with aryl halides under mild conditions (O °C). , 2013, Journal of the American Chemical Society.

[51]  Gianluca Accorsi,et al.  Luminescent ionic transition-metal complexes for light-emitting electrochemical cells. , 2012, Angewandte Chemie.

[52]  D. J. Robbins,et al.  Luminescent metal complexes. Part 1. Tris-chelates of substituted 2,2′-bipyridyls with ruthenium (II) as dyes for luminescent solar collectors , 1984 .

[53]  D. Schuster,et al.  Porphyrin–fullerene photosynthetic model systems with rotaxane and catenane architectures , 2006 .

[54]  D. McMillin,et al.  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. , 2002, Inorganic chemistry.

[55]  Qisheng Zhang,et al.  Highly Efficient Green Phosphorescent Organic Light‐Emitting Diodes Based on CuI Complexes , 2004 .

[56]  C. Duhayon,et al.  Synthesis and Photophysical Properties of Copper(I) Complexes Obtained from 1,10-Phenanthroline Ligands with Increasingly Bulky 2,9-Substituents , 2010 .

[57]  Alexander J. M. Miller,et al.  E-type delayed fluorescence of a phosphine-supported Cu2(mu-NAr2)2 diamond core: harvesting singlet and triplet excitons in OLEDs. , 2010, Journal of the American Chemical Society.

[58]  C. Housecroft,et al.  Light harvesting with Earth abundant d-block metals: Development of sensitizers in dye-sensitized solar cells (DSCs) , 2013 .

[59]  T. Tahara,et al.  Real-time observation of the photoinduced structural change of bis(2,9-dimethyl-1,10-phenanthroline)copper(I) by femtosecond fluorescence spectroscopy: a realistic potential curve of the Jahn-Teller distortion. , 2007, Journal of the American Chemical Society.

[60]  M. Sliwa,et al.  New heteroleptic bis-phenanthroline copper(I) complexes with dipyridophenazine or imidazole fused phenanthroline ligands: spectral, electrochemical, and quantum chemical studies. , 2011, Inorganic chemistry.

[61]  D. Schuster,et al.  Photoinduced electron transfer in porphyrin- and fullerene/porphyrin-based rotaxanes as studied by time-resolved EPR spectroscopy. , 2009, The journal of physical chemistry. A.

[62]  Martin Nieger,et al.  Synthesis, structure, and characterization of dinuclear copper(I) halide complexes with P^N ligands featuring exciting photoluminescence properties. , 2013, Inorganic chemistry.

[63]  N. McClenaghan,et al.  Improving the photophysical properties of copper(I) bis(phenanthroline) complexes , 2008 .

[64]  Vivian Wing-Wah Yam,et al.  Luminescent polynuclear d10 metal complexes , 1999 .

[65]  Hartmut Yersin,et al.  Highly efficient thermally activated fluorescence of a new rigid Cu(I) complex [Cu(dmp)(phanephos)]+. , 2013, Dalton transactions.

[66]  Alexander J. M. Miller,et al.  Probing the electronic structures of [Cu2(mu-XR2)]n+ diamond cores as a function of the bridging X atom (X = N or P) and charge (n = 0, 1, 2). , 2008, Journal of the American Chemical Society.

[67]  D. McMillin,et al.  Reductive Quenching of Photoexcited Cu(dipp)(2)(+) and Cu(tptap)(2)(+) by Ferrocenes (dipp = 2,9-Diisopropyl-1,10-phenanthroline and tptap = 2,3,6,7-Tetraphenyl-1,4,5,8-tetraazaphenanthrene). , 1998, Inorganic chemistry.

[68]  G. Meyer,et al.  MLCT excited states of cuprous bis-phenanthroline coordination compounds , 2000 .

[69]  Canzhong Lu,et al.  Rational Design of Strongly Blue-Emitting Cuprous Complexes with Thermally Activated Delayed Fluorescence and Application in Solution-Processed OLEDs , 2013 .

[70]  D. Schuster,et al.  [60]fullerene-stoppered porphyrinorotaxanes: pronounced elongation of charge-separated-state lifetimes. , 2004, Journal of the American Chemical Society.

[71]  K. Gordon,et al.  Synthesis, characterization, and photophysics of oxadiazole- and diphenylaniline-substituted Re(I) and Cu(I) complexes. , 2013, Inorganic chemistry.

[72]  Masashi Hashimoto,et al.  Highly efficient green organic light-emitting diodes containing luminescent tetrahedral copper(I) complexes , 2013 .

[73]  M. Puchalska,et al.  Solid state luminescence of CuI and CuNCS complexes with phenanthrolines and a new tris (aminomethyl) phosphine derived from N-methyl-2-phenylethanamine , 2014 .

[74]  P. Cox,et al.  Copper(I) complexes of 1,10-phenanthroline and heterocyclic thioamides: an experimental and theoretical (DFT) investigation of the photophysical characteristics. , 2013, Dalton transactions.

[75]  D. Schuster,et al.  Topological and Conformational Effects on Electron Transfer Dynamics in Porphyrin-[60]Fullerene Interlocked Systems. , 2012, Chemistry of materials : a publication of the American Chemical Society.

[76]  N. Armaroli Photoactive mono- and polynuclear Cu(I)–phenanthrolines. A viable alternative to Ru(II)–polypyridines? , 2001 .

[77]  N. Armaroli,et al.  Highly Luminescent CuI Complexes for Light‐Emitting Electrochemical Cells , 2006 .

[78]  R. Compton,et al.  The electro-oxidation of N,N-dimethyl-p-toluidine in acetonitrile:: a microdisk voltammetry study , 2002 .

[79]  M. Boujtita,et al.  First application of the HETPHEN concept to new heteroleptic bis(diimine) copper(I) complexes as sensitizers in dye sensitized solar cells. , 2013, Dalton transactions.

[80]  A. Listorti,et al.  Novel phenanthroline ligands and their kinetically locked copper(I) complexes with unexpected photophysical properties. , 2006, Inorganic chemistry.

[81]  Masashi Hashimoto,et al.  Highly efficient green organic light-emitting diodes containing luminescent three-coordinate copper(I) complexes. , 2011, Journal of the American Chemical Society.

[82]  N. Robertson CuI versus RuII: dye-sensitized solar cells and beyond. , 2008, ChemSusChem.

[83]  K. Gordon,et al.  Heteroleptic Cu(I) bis-diimine complexes of 6,6'-dimesityl-2,2'-bipyridine: a structural, theoretical and spectroscopic study. , 2013, Inorganic chemistry.

[84]  P. Gantzel,et al.  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) , 1999 .

[85]  Andreas F. Rausch,et al.  The triplet state of organo-transition metal compounds. Triplet harvesting and singlet harvesting for efficient OLEDs , 2011 .

[86]  W. R. Robinson,et al.  Steric effects and the behavior of Cu(NN)(PPh3)2+ systems in fluid solution. Crystal and molecular structures of [Cu(dmp)(PPh3)2]NO3 and [Cu(phen)(PPh3)2]NO3.1.5EtOH , 1985 .

[87]  C. M. Elliott,et al.  Photoinduced multistep charge separation in a heteroleptic Cu(I) bis(phenanthroline)-based donor-chromophore-acceptor triad. , 2012, Journal of the American Chemical Society.

[88]  C. Kelly,et al.  Tuning charge recombination rate constants through inner-sphere coordination in a copper(I) donor-acceptor compound. , 2000, Inorganic chemistry.

[89]  T. Swager,et al.  CONDUCTING POLYMETALLOROTAXANES : A SUPRAMOLECULAR APPROACH TO TRANSITION METAL ION SENSORS , 1996 .

[90]  D. McMillin,et al.  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 , 1987 .

[91]  A. Listorti,et al.  Photochemistry and Photophysics of Coordination Compounds: Copper , 2007 .

[92]  F. Castellano,et al.  Synthesis and characterization of tris(heteroleptic) Ru(II) complexes bearing styryl subunits. , 2011, Inorganic chemistry.

[93]  C. Kelly,et al.  Electron and energy transfer from CuI MLCT excited states , 1998 .

[94]  M. Beller,et al.  Photocatalytic water reduction with copper-based photosensitizers: a noble-metal-free system. , 2013, Angewandte Chemie.

[95]  Tahei Tahara,et al.  Coherent nuclear dynamics in ultrafast photoinduced structural change of bis(diimine)copper(I) complex. , 2011, Journal of the American Chemical Society.

[96]  D. McMillin,et al.  Simple Cu(I) complexes with unprecedented excited-state lifetimes. , 2002, Journal of the American Chemical Society.

[97]  Peng Wang,et al.  A high molar extinction coefficient sensitizer for stable dye-sensitized solar cells. , 2005, Journal of the American Chemical Society.

[98]  C. Adachi,et al.  Design of efficient thermally activated delayed fluorescence materials for pure blue organic light emitting diodes. , 2012, Journal of the American Chemical Society.

[99]  Massimo Marcaccio,et al.  New tetrazole-based Cu(I) homo- and heteroleptic complexes with various P^P ligands: synthesis, characterization, redox and photophysical properties. , 2013, Dalton transactions.

[100]  M. Beller,et al.  A noble-metal-free system for photocatalytic hydrogen production from water. , 2013, Chemistry.

[101]  K. Gordon,et al.  Structural, electronic and computational studies of heteroleptic Cu(I) complexes of 6,6′-dimesityl-2,2′-bipyridine with sulfur-substituted dipyridophenazine ligands , 2013 .

[102]  S. Ng,,et al.  Luminescent metal-organic frameworks (MOFs) as a chemopalette: tuning the thermochromic behavior of dual-emissive phosphorescence by adjusting the supramolecular microenvironments. , 2013, Chemistry.

[103]  Nicola Armaroli,et al.  Heteroleptic copper(I) complexes prepared from phenanthroline and bis-phosphine ligands. , 2013, Inorganic chemistry.

[104]  C. Housecroft,et al.  Towards Sustainable Dyes for Dye-Sensitized Solar Cells , 2009 .

[105]  D. Schuster,et al.  Convergent synthesis and photoinduced processes in multi-chromophoric rotaxanes. , 2010, The journal of physical chemistry. B.

[106]  Kiyoshi Tsuge,et al.  Luminescent Complexes Containing Halogeno-bridged Dicopper(I) Unit {Cu2(µ-X)2} (X = Cl, Br, and I) , 2013 .

[107]  Jean-Pierre Sauvage,et al.  Interlacing molecular threads on transition metals: catenands, catenates, and knots , 1990 .

[108]  M. Grätzel,et al.  Phenomenally high molar extinction coefficient sensitizer with "donor-acceptor" ligands for dye-sensitized solar cell applications. , 2008, Inorganic chemistry.

[109]  T. Meyer,et al.  Photochemistry of Ru( bpy)32+. Solvent Effects , 1983 .

[110]  C. Sinha,et al.  Structure, fluorescence, redox properties and theoretical interpretation of heteroleptic copper(I) and silver(I) complexes of N-[(2-pyridyl)methyliden]-6-coumarin and triphenylphosphine , 2014 .

[111]  D. McMillin,et al.  Cooperative Substituent Effects on the Excited States of Copper Phenanthrolines. , 1999, Inorganic chemistry.

[112]  C. Kelly,et al.  Long-Lived Charge-Separated States Following Light Excitation of Cu(I) Donor−Acceptor Compounds , 1997 .

[113]  A. Gewirth,et al.  Cu complexes that catalyze the oxygen reduction reaction , 2013 .

[114]  D. Schuster,et al.  [2]Catenanes decorated with porphyrin and [60]fullerene groups: design, convergent synthesis, and photoinduced processes. , 2010, Journal of the American Chemical Society.

[115]  A. Listorti,et al.  Heteroleptic copper(I) complexes coupled with methano[60]fullerene: synthesis, electrochemistry, and photophysics. , 2008, Inorganic chemistry.

[116]  D. Schuster,et al.  Photoinduced Processes in Some Mechanically Interlocked Supramolecules as Studied by Time-Resolved Electron Paramagnetic Resonance , 2011 .

[117]  M. Schmittel,et al.  Stable mixed phenanthroline copper(i) complexes. Key building blocks for supramolecular coordination chemistry , 1997 .

[118]  J. Burstyn,et al.  Photophysical characteristics and reactivity of bis(2,9-di-tert-butyl-1,10-phenanthroline)copper(I). , 2009, Inorganic chemistry.