Engineering of efficient phosphorescent iridium cationic complex for developing oxygen-sensitive polymeric and nanostructured films.

In this study, a novel phosphorescent Ir(III) complex [Ir(2-phenylpyridine)2(4,4'-bis(2-(4-N,N-methylhexylaminophenyl)ethyl)-2-2'-bipyridine)Cl] (for convenience, the complex was given the synonym N-948) has been designed and synthesized, to be used as an oxygen probe. It was characterized by spectroscopic and analytical methods when incorporated in a polystyrene and nanostructured metal oxide support. N-948 is the first Ir complex in the literature with a luminescence emission at a wavelength higher than 650 nm (665 nm), with a quantum yield higher than 0.50 (0.58 +/- 0.05) and an extremely long phosphorescence lifetime (102 micros) which has been used for developing oxygen-sensitive films. In addition, the new complex shows a Stern-Volmer constant which is 20 times higher than that of other Ir complexes known from the literature when they are immobilized in polystyrene. The sensing film shows long-term stability (up to 12 months), complete reversibility of the signal quenched by oxygen and a quick response time to various oxygen concentrations (<2 s changing from 10 vol% pO2 to 90 vol% pO2). Thus, it is an interesting and promising complex for developing oxygen-selective sensors for gas analysis and the analysis of dissolved oxygen.

[1]  Peipei Sun,et al.  New Iridium Complexes as Highly Efficient Orange–Red Emitters in Organic Light‐Emitting Diodes , 2003 .

[2]  D. Buckley,et al.  A cell viability assay based on monitoring respiration by optical oxygen sensing. , 2000, Analytical biochemistry.

[3]  Dmitri B. Papkovsky,et al.  Study of migration of active components of phosphorescent oxygen sensors for food packaging applications , 2005 .

[4]  Ichiro Okura,et al.  Green luminescent iridium(III) complex immobilized in fluoropolymer film as optical oxygen-sensing material , 2001 .

[5]  J. Kerry,et al.  Assessment of oxygen levels in convenience‐style muscle‐based sous vide products through optical means and impact on shelf‐life stability , 2004 .

[6]  Benjamin A. DeGraff,et al.  Photophysics and photochemistry of oxygen sensors based on luminescent transition-metal complexes , 1991 .

[7]  Alan J. Lough,et al.  Evaluation of Phosphorescent Rhenium and Iridium Complexes in Polythionylphosphazene Films for Oxygen Sensor Applications , 2005 .

[8]  A. Crispini,et al.  Cationic Cyclometalated Iridium Luminophores: Photophysical, Redox, and Structural Characterization , 2004 .

[9]  W. Rumsey,et al.  Imaging of phosphorescence: a novel method for measuring oxygen distribution in perfused tissue. , 1988, Science.

[10]  D Murphy,et al.  Highly phosphorescent bis-cyclometalated iridium complexes: synthesis, photophysical characterization, and use in organic light emitting diodes. , 2001, Journal of the American Chemical Society.

[11]  M. Lanza,et al.  Luminescent Mononuclear and Dinuclear Iridium(III) Cyclometalated Complexes Immobilized in a Polymeric Matrix as Solid-State Oxygen Sensors. , 1998, Analytical chemistry.

[12]  F. Puntoriero,et al.  Ionic luminescent cyclometalated Ir(III) complexes with polypyridine co-ligands , 2006 .

[13]  Wolfgang Kern,et al.  Novel oxygen optrode withstanding autoclavation: technical solutions and performance , 2001 .

[14]  I. Samuel,et al.  Tuning the emission of cyclometalated iridium complexes by simple ligand modification , 2003 .

[15]  Y. Amao,et al.  Probes and Polymers for Optical Sensing of Oxygen , 2003 .

[16]  Christoph Abels,et al.  In Vivo Phosphorescence Imaging of pO2 Using Planar Oxygen Sensors , 2005, Microcirculation.

[17]  Daniel J. Bartnik,et al.  Performance and use of paracorporeal fiber optic blood gas sensors , 1994, Photonics West - Lasers and Applications in Science and Engineering.

[18]  Maria C DeRosa,et al.  Iridium luminophore complexes for unimolecular oxygen sensors. , 2004, Journal of the American Chemical Society.

[19]  U. Spichiger-Keller,et al.  Large Area, Nanoparticulate Metal Oxide Coatings for Consumer Nanotechnologies , 2007 .

[20]  C. Shu,et al.  Tuning the emission and morphology of cyclometalated iridium complexes and their applications to organic light-emitting diodes , 2005 .

[21]  Simona Garon,et al.  Cationic bis-cyclometalated iridium(III) diimine complexes and their use in efficient blue, green, and red electroluminescent devices. , 2005, Inorganic chemistry.

[22]  I. Manners,et al.  Covalent Attachment of RuII Phenanthroline Complexes to Polythionylphosphazenes: The Development and Evaluation of Single-Component Polymeric Oxygen Sensors , 2002 .

[23]  Ursula E. Spichiger-Keller,et al.  Novel oxygen sensitive complexes for optical oxygen sensing. , 2007, Talanta.

[24]  J. Lakowicz Principles of fluorescence spectroscopy , 1983 .

[25]  P. Hauser,et al.  All-solid-state instrument for fluorescence-based fibre-optic chemical sensors , 1993 .

[26]  U. Spichiger-Keller,et al.  Novel optical NO2-selective sensor based on phthalocyaninato-iron(II) incorporated into a nanostructured matrix , 2006 .

[27]  Sergey Lamansky,et al.  Synthesis and characterization of phosphorescent cyclometalated platinum complexes. , 2001, Inorganic chemistry.

[28]  Ingo Klimant,et al.  Optical Fiber Sensor for Biological Oxygen Demand , 1994 .

[29]  C. Shu,et al.  Iridium(III) complexes with orthometalated quinoxaline ligands: subtle tuning of emission to the saturated red color. , 2005, Inorganic chemistry.

[30]  Ursula E. Spichiger-Keller,et al.  Novel nanostructured materials to develop oxygen-sensitive films for optical sensors , 2006 .

[31]  Chunhui Huang,et al.  Red Phosphorescent Iridium Complex Containing Carbazole‐Functionalized β‐Diketonate for Highly Efficient Nondoped Organic Light‐Emitting Diodes , 2006 .

[32]  Ichiro Okura,et al.  Optical oxygen sensing materials: chemisorption film of ruthenium(II) polypyridyl complexes attached to anionic polymer , 2003 .

[33]  Ursula E. Spichiger-Keller,et al.  Second Generation Nanostructured Metal Oxide Matrices to Increase the Thermal Stability of CO and NO2 Sensing Layers Based on Iron(II) Phthalocyanine , 2007 .

[34]  M. DeRosa,et al.  Synthesis, characterization, and evaluation of [Ir(ppy)2(vpy)Cl] as a polymer-bound oxygen sensor. , 2003, Inorganic chemistry.

[35]  C. Jiang,et al.  High‐Efficiency, Saturated Red‐Phosphorescent Polymer Light‐Emitting Diodes Based on Conjugated and Non‐Conjugated Polymers Doped with an Ir Complex , 2004 .

[36]  E. Terrill,et al.  A micro-hole potentiostatic oxygen sensor for oceanic CTDs , 1995 .