Porous phosphorescent coordination polymers for oxygen sensing.

Phosphorescent cyclometalated iridium tris(2-phenylpyridine) derivatives were designed and incorporated into coordination polymers as tricarboxylate bridging ligands. Three different crystalline coordination polymers were synthesized using a solvothermal technique and were characterized using a variety of methods, including single-crystal X-ray diffraction, PXRD, TGA, IR spectroscopy, gas adsorption measurements, and luminescence measurements. The coordination polymer built from Ir[3-(2-pyridyl)benzoate](3), 1, was found to be highly porous with a nitrogen BET surface area of 764 m(2)/g, whereas the coordination polymers built from Ir[4-(2-pyridyl)benzoate](3), 2 and 3, were nonporous. The (3)MLCT phosphorescence of each of the three coordination polymers was quenched in the presence of O(2). However, only 1 showed quick and reversible luminescence quenching by oxygen, whereas 2 and 3 exhibited gradual and irreversible luminescence quenching by oxygen. The high permanent porosity of 1 allows for rapid diffusion of oxygen through the open channels, leading to efficient and reversible quenching of the (3)MLCT phosphorescence. This work highlights the opportunity of designing highly porous and luminescent coordination polymers for sensing other important analytes.

[1]  Jianping Ma,et al.  Tunable luminescent lanthanide coordination polymers based on reversible solid-state ion-exchange monitored by ion-dependent photoinduced emission spectra. , 2007, Journal of the American Chemical Society.

[2]  Wenbin Lin,et al.  Modular synthesis of functional nanoscale coordination polymers. , 2009, Angewandte Chemie.

[3]  M. Allendorf,et al.  Luminescent metal-organic frameworks. , 2009, Chemical Society reviews.

[4]  Wenbin Lin,et al.  Luminescent Lanthanide Coordination Polymers , 1999 .

[5]  Wenbin Lin,et al.  Highly interpenetrated metal-organic frameworks for hydrogen storage. , 2004, Angewandte Chemie.

[6]  Omar K Farha,et al.  Metal-organic framework materials as catalysts. , 2009, Chemical Society reviews.

[7]  Wenbin Lin,et al.  Crystal engineering of NLO materials based on metal--organic coordination networks. , 2002, Accounts of chemical research.

[8]  Wai Kin Chan,et al.  Exceptional Oxygen Sensing Capabilities and Triplet State Properties of Ir(ppy-NPh2)3 , 2009 .

[9]  J. Long,et al.  Hydrogen storage in microporous metal-organic frameworks with exposed metal sites. , 2008, Angewandte Chemie.

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

[11]  D. Olson,et al.  A luminescent microporous metal-organic framework for the fast and reversible detection of high explosives. , 2009, Angewandte Chemie.

[12]  Kunlun Hong,et al.  Surface interactions and quantum kinetic molecular sieving for H2 and D2 adsorption on a mixed metal-organic framework material. , 2008, Journal of the American Chemical Society.

[13]  Wenbin Lin,et al.  Enantioselective catalysis with homochiral metal-organic frameworks. , 2009, Chemical Society reviews.

[14]  M. Thompson The Evolution of Organometallic Complexes in Organic Light-Emitting Devices , 2007 .

[15]  Omar M Yaghi,et al.  Strategies for hydrogen storage in metal--organic frameworks. , 2005, Angewandte Chemie.

[16]  Weili Lin,et al.  Nanoscale metal-organic frameworks as potential multimodal contrast enhancing agents. , 2006, Journal of the American Chemical Society.

[17]  C. Cahill,et al.  Homo- and heterometallic coordination polymers from the f elements , 2007 .

[18]  S. Nguyen,et al.  A metal-organic framework material that functions as an enantioselective catalyst for olefin epoxidation. , 2006, Chemical communications.

[19]  Guodong Qian,et al.  A luminescent microporous metal-organic framework for the recognition and sensing of anions. , 2008, Journal of the American Chemical Society.

[20]  Yuanjing Cui,et al.  A luminescent metal-organic framework with Lewis basic pyridyl sites for the sensing of metal ions. , 2009, Angewandte Chemie.