N‐Heterocyclic Carbene Complexes of Iron as Photosensitizers for Light‐Induced Water Reduction

For the first time, the potential of noble-metal-free iron-based photosensitizers for photocatalytic water reduction by using homo- and heteroleptic carbene complexes was proven. The development of a facile synthesis route for such carbene complexes was delineated. The complexes were investigated by UV/Vis and fluorescence spectroscopy, DFT calculations, cyclic voltammetry, and X-ray absorption spectroscopy. Their catalytic performance was compared to that of established noble-metal-containing photosensitizers such as [Ir(ppy)2(bpy)][PF6] (Hppy = 2-phenylpyridine, bpy = 2,2′-bipyridine).

[1]  V. Sundström,et al.  Fe N-Heterocyclic Carbene Complexes as Promising Photosensitizers. , 2016, Accounts of chemical research.

[2]  M. Beller,et al.  Efficient Photocatalytic Water Reduction Using In Situ Generated Knölker's Iron Complexes , 2016 .

[3]  Lisa A. Fredin,et al.  Iron sensitizer converts light to electrons with 92% yield. , 2015, Nature chemistry.

[4]  I. Dixon,et al.  Reversing the relative 3MLCT-3MC order in Fe(ii) complexes using cyclometallating ligands: a computational study aiming at luminescent Fe(ii) complexes. , 2015, Dalton transactions.

[5]  I. Dixon,et al.  Probing the photophysical capability of mono and bis(cyclometallated) Fe(ii) polypyridine complexes using inexpensive ground state DFT. , 2014, Dalton transactions.

[6]  X. Assfeld,et al.  Heteroleptic Pyridyl‐Carbene Iron Complexes with Tuneable Electronic Properties , 2014 .

[7]  Lisa A. Fredin,et al.  Exceptional Excited-State Lifetime of an Iron(II)-N-Heterocyclic Carbene Complex Explained. , 2014, The journal of physical chemistry letters.

[8]  M. Sliwa,et al.  An efficient Ru(II) -Rh(III) -Ru(II) polypyridyl photocatalyst for visible-light-driven hydrogen production in aqueous solution. , 2014, Angewandte Chemie.

[9]  I. Sazanovich,et al.  Photocatalytic hydrogen production from a noble metal free system based on a water soluble porphyrin derivative and a cobaloxime catalyst. , 2014, Chemical communications.

[10]  I. Dixon,et al.  The (N4C2)2- donor set as promising motif for bis(tridentate) iron(II) photoactive compounds. , 2013, Inorganic chemistry.

[11]  Soo Young Park,et al.  Highly efficient photocatalytic water reduction with robust iridium(III) photosensitizers containing arylsilyl substituents. , 2013, Angewandte Chemie.

[12]  F. Molton,et al.  Efficient photocatalytic hydrogen production in water using a cobalt(III) tetraaza-macrocyclic catalyst: electrochemical generation of the low-valent Co(I) species and its reactivity toward proton reduction. , 2013, Physical chemistry chemical physics : PCCP.

[13]  C. Chiorboli,et al.  Porphyrin-cobaloxime dyads for photoinduced hydrogen production: investigation of the primary photochemical process , 2013, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[14]  V. Sundström,et al.  Towards longer-lived metal-to-ligand charge transfer states of iron(II) complexes: an N-heterocyclic carbene approach. , 2013, Chemical communications.

[15]  Yongjun Yuan,et al.  Charge-neutral amidinate-containing iridium complexes capable of efficient photocatalytic water reduction. , 2013, Chemistry.

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

[17]  Patrick L. Holland,et al.  Robust Photogeneration of H2 in Water Using Semiconductor Nanocrystals and a Nickel Catalyst , 2012, Science.

[18]  M. Hu,et al.  Efficient [FeFe] hydrogenase mimic dyads covalently linking to iridium photosensitizer for photocatalytic hydrogen evolution. , 2012, Dalton transactions.

[19]  Louis J. Farrugia,et al.  WinGX and ORTEP for Windows: an update , 2012 .

[20]  K. Sakai,et al.  Photoinduced hydrogen evolution from water by a simple platinum(II) terpyridine derivative: a Z-scheme photosynthesis. , 2012, Angewandte Chemie.

[21]  Xien Liu,et al.  Transition metal complexes that catalyze oxygen formation from water: 1979–2010 , 2012 .

[22]  Xuesong Wang,et al.  Large improvement in the catalytic activity due to small changes in the diimine ligands: new mechanistic insight into the dirhodium(II,II) complex-based photocatalytic H2 production. , 2012, Inorganic chemistry.

[23]  Travis A. White,et al.  Efficient photocatalytic hydrogen production in a single-component system using Ru,Rh,Ru supramolecules containing 4,7-diphenyl-1,10-phenanthroline. , 2011, Angewandte Chemie.

[24]  R. Groarke,et al.  The effect of peripheral bipyridine ligands on the photocatalytic hydrogen production activity of Ru/Pd catalysts. , 2011, Dalton transactions.

[25]  R. Ludwig,et al.  Photocatalytic hydrogen generation from water with iron carbonyl phosphine complexes: improved water reduction catalysts and mechanistic insights. , 2011, Chemistry.

[26]  Travis A. White,et al.  A new structural motif for photoinitiated electron collection: Ru,Rh bimetallics providing insight into H2 production via photocatalysis of water reduction by Ru,Rh,Ru supramolecules. , 2011, Chemical communications.

[27]  K. Sakai,et al.  Light-induced charge separation and photocatalytic hydrogen evolution from water using Ru(II)Pt(II)-based molecular devices: effects of introducing additional donor and/or acceptor sites. , 2011, Dalton transactions.

[28]  P. Hamm,et al.  Photocatalytic H2 production from water with rhenium and cobalt complexes. , 2011, Inorganic chemistry.

[29]  F. Castellano,et al.  Homogeneous photocatalytic hydrogen production using π-conjugated platinum(II) arylacetylide sensitizers. , 2011, Inorganic chemistry.

[30]  J. Otsuki,et al.  Photocatalytic hydrogen production from water in self-assembled supramolecular iridium-cobalt systems. , 2010, Chemical communications.

[31]  S. Bernhard,et al.  Robust photocatalytic water reduction with cyclometalated Ir(III) 4-vinyl-2,2'-bipyridine complexes. , 2010, Chemical communications.

[32]  Szu-Hsueh Lai,et al.  Dynamics of the excited states of [Ir(ppy)2bpy]+ with triple phosphorescence. , 2010, The journal of physical chemistry. A.

[33]  Y. Amao,et al.  Hydrolysis of a mixture of saccharides by cellulase from Aspergillus niger and its application for visible-light-induced hydrogen gas production system using Mg chlorophyll-a and platinum nanoparticles , 2010 .

[34]  Benjamin Dietzek,et al.  Photochemisches Schicksal: Der erste Schritt bestimmt die Effizienz der H2‐Bildung mit einem supramolekularen Photokatalysator , 2010 .

[35]  B. Dietzek,et al.  Photochemical fate: the first step determines efficiency of H2 formation with a supramolecular photocatalyst. , 2010, Angewandte Chemie.

[36]  S. Ott,et al.  High-turnover photochemical hydrogen production catalyzed by a model complex of the [FeFe]-hydrogenase active site. , 2010, Chemistry.

[37]  F. Gärtner,et al.  Eisencarbonyle: effiziente Katalysatoren für die lichtgetriebene Wasserstofferzeugung aus Wasser , 2009 .

[38]  M. Beller,et al.  Light-driven hydrogen generation: efficient iron-based water reduction catalysts. , 2009, Angewandte Chemie.

[39]  H. Yamaguchi,et al.  Photoinduced Hydrogen-Evolution System with an Antibody–Porphyrin Complex as a Photosensitizer , 2009 .

[40]  S. Ott,et al.  Introducing a dark reaction to photochemistry: photocatalytic hydrogen from [FeFe] hydrogenase active site model complexes. , 2009, Dalton transactions.

[41]  Y. Amao,et al.  Photoinduced Hydrogen Production with Artificial Photosynthesis System Based on Carotenoid−Chlorophyll Conjugated Micelles , 2009 .

[42]  Licheng Sun,et al.  Light-driven hydrogen production catalysed by transition metal complexes in homogeneous systems. , 2009, Dalton transactions.

[43]  Jürgen Popp,et al.  Photophysics of an intramolecular hydrogen-evolving Ru-Pd photocatalyst. , 2009, Chemistry.

[44]  S. Bernhard,et al.  Structure-activity correlations among iridium(III) photosensitizers in a robust water-reducing system. , 2009, Inorganic chemistry.

[45]  S. Bernhard,et al.  Photon-driven catalytic proton reduction with a robust homoleptic iridium(III) 6-phenyl-2,2'-bipyridine complex ([Ir(C--N--N)(2)](+)). , 2009, Inorganic chemistry.

[46]  Pingwu Du,et al.  Making hydrogen from water using a homogeneous system without noble metals. , 2009, Journal of the American Chemical Society.

[47]  S. Bernhard,et al.  Progress towards solar-powered homogeneous water photolysis , 2009 .

[48]  J. Schneider,et al.  Visible light-driven hydrogen production from aqueous protons catalyzed by molecular cobaloxime catalysts. , 2009, Inorganic chemistry.

[49]  Shamindri M. Arachchige,et al.  Design considerations for a system for photocatalytic hydrogen production from water employing mixed-metal photochemical molecular devices for photoinitiated electron collection. , 2009, Inorganic chemistry.

[50]  S. Bernhard,et al.  Homogeneous catalytic system for photoinduced hydrogen production utilizing iridium and rhodium complexes. , 2008, Inorganic chemistry.

[51]  Pingwu Du,et al.  A homogeneous system for the photogeneration of hydrogen from water based on a platinum(II) terpyridyl acetylide chromophore and a molecular cobalt catalyst. , 2008, Journal of the American Chemical Society.

[52]  Mei Wang,et al.  Visible light-driven electron transfer and hydrogen generation catalyzed by bioinspired [2Fe2S] complexes. , 2008, Inorganic chemistry.

[53]  Vincenzo Balzani,et al.  Photochemical conversion of solar energy. , 2008, ChemSusChem.

[54]  S. Bernhard,et al.  Visible light induced catalytic water reduction without an electron relay. , 2007, Chemistry.

[55]  S. Bernhard,et al.  Synthetically tailored excited states: phosphorescent, cyclometalated iridium(III) complexes and their applications. , 2006, Chemistry.

[56]  Y. Amao,et al.  Photoinduced hydrogen production with chlorophyll-platinum nano-conjugated micellar system , 2006 .

[57]  M. Haga,et al.  A photo-hydrogen-evolving molecular device driving visible-light-induced EDTA-reduction of water into molecular hydrogen. , 2006, Journal of the American Chemical Society.

[58]  George G. Malliaras,et al.  Single-Layer Electroluminescent Devices and Photoinduced Hydrogen Production from an Ionic Iridium(III) Complex , 2005 .

[59]  Jonas I. Goldsmith,et al.  Discovery and high-throughput screening of heteroleptic iridium complexes for photoinduced hydrogen production. , 2005, Journal of the American Chemical Society.

[60]  J. Steed,et al.  Bis(carbene)pyridine Complexes of the Early to Middle Transition Metals: Survey of Ethylene Oligomerization and Polymerization Capability , 2004 .

[61]  Y. Amao,et al.  Effect of micellar species on photoinduced hydrogen production with Mg chlorophyll-a from spirulina and colloidal platinum , 2004 .

[62]  Joseph A. Wright,et al.  N-Heterocyclic Pincer Dicarbene Complexes of Iron(II): C-2 and C-5 Metalated Carbenes on the Same Metal Center , 2004 .

[63]  Licheng Sun,et al.  Synthesis and structure of a biomimetic model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer. , 2003, Angewandte Chemie.

[64]  I. Tabata,et al.  Hydrogen evolution sensitized by tin-porphyrin in microheterogeneous systems , 2002 .

[65]  P. Power,et al.  Three-coordinate iron complexes: x-ray structural characterization of the iron amide-bridged dimers [Fe(NR2)2]2 (R = SiMe3, C6H5) and the adduct Fe[N(SiMe3)2]2(THF) and determination of the association energy of the monomer Fe{N(SiMe3)2}2 in solution , 1991 .

[66]  J. Lyklema,et al.  A kinetic model for the Ru(bipy)32+/MV2+/EDTA/colloidal RuO2 system for photogeneration of hydrogen , 1988 .

[67]  T. Meyer.  Photochemistry of metal coordination complexes: metal to ligand charge transfer excited states , 1986 .

[68]  G. Mclendon,et al.  Model systems for photocatalytic water reduction: role of pH and metal colloid catalysts , 1981 .

[69]  J. Lehn,et al.  Hydrogen Generation by Visible Light Irradiation of Aqueous Solutions of Metal Complexes. An approach to the photochemical conversion and storage of solar energy , 1979 .

[70]  B. Brunschwig,et al.  Homogeneous catalysis of the photoreduction of water by visible light. Mediation by a tris(2,2'-bipyridine)ruthenium(II)-cobalt(II) macrocycle system , 1979 .

[71]  M. Grätzel,et al.  Hydrogen Evolution from Water by Visible Light, a Homogeneous Three Component Test System for Redox Catalysis , 1978 .

[72]  V. Balzani,et al.  Solar Energy Conversion by Water Photodissociation , 1975, Science.

[73]  W. E. Ohnesorge,et al.  Temperature effects on charge-transfer luminescence intensity of some transition metal ion chelates , 1969 .

[74]  M. Pohl,et al.  Investigation and enhancement of the stability and performance of water reduction systems based on cyclometalated iridium(III) complexes. , 2013, ChemSusChem.

[75]  Vincenzo Balzani,et al.  The future of energy supply: Challenges and opportunities. , 2007, Angewandte Chemie.

[76]  Vincenzo Balzani,et al.  Die Zukunft der Energieversorgung – Herausforderungen und Chancen , 2007 .

[77]  Y. Amao,et al.  Biohydrogen production with the light-harvesting function of grana from spirulina and colloidal platinum , 2006 .

[78]  Y. Amao,et al.  Biohydrogen production from sucrose using the visible light sensitization of artificial Zn chlorophyll-a. , 2003, Bioconjugate chemistry.

[79]  Y. Amao,et al.  Photoinduced Hydrogen Production from D-Maltose in the Presence of Chlorophyll a and Pt Colloid , 2003 .

[80]  E. Amouyal.  Photochemical production of hydrogen and oxygen from water: A review and state of the art , 1995 .