000185450 001__ 185450
000185450 005__ 20181203023045.0
000185450 0247_ $$2doi$$a10.1021/om300894m
000185450 022__ $$a0276-7333
000185450 02470 $$2ISI$$a000314332100013
000185450 037__ $$aARTICLE
000185450 245__ $$aExtreme Tuning of Redox and Optical Properties of Cationic Cyclometalated Iridium(III) Isocyanide Complexes
000185450 260__ $$bAmerican Chemical Society$$c2013$$aWashington
000185450 269__ $$a2013
000185450 300__ $$a8
000185450 336__ $$aJournal Articles
000185450 520__ $$aWe report seven heteroleptic cationic iridium(III) complexes with cyclometalating N-arylazoles and alkyl/aryl isocyanides, [((CN)-N-boolean AND)(2)Ir(CNR)(2)](CF3SO3), and characterize two of them by crystal structure analysis. The complexes are air- and moisture-stable white solids that have electronic transitions at very high energy with absorption onset at 320-380 nm. The complexes are difficult to reduce and oxidize; they exhibit irreversible electrochemical processes with peak potentials (against ferrocene) at -2.74 to -2.37 V (reduction) and 0.99-1.56 V (oxidation) and have a large redox gap of 3.49-4.26 V. The reduction potential of the complex is determined by the azole heterocycle (pyrazole or indazole) and by the isocyanide (tert-butyl or 2,6-dimethylphenyl) and the oxidation potential by the Ir-aryl fragment [aryl = 2',4'-R-2-phenyl (R = H/F), 9',9'-dihexy1-2'-fluorenyl]. Three of the complexes exhibit phosphorescence in argon-saturated dichloromethane and acetonitrile solutions at room temperature with 0-0 transitions at 473-478 nm (green color; the emission spectra are solvent-independent), quantum yields of 3-25%, and long excited-state lifetimes of 62-350 mu s. All of the complexes are phosphorescent at 77 K with 0-0 transitions at 387-474 nm (blue to green color). The extremely long calculated radiative lifetimes, 0.5-3.5 ms, confirm that the complexes emit from a cyclometalating-ligand-centered excited state.
000185450 700__ $$0244226$$g178166$$uEcole Polytech Fed Lausanne, Lab Photon & Interfaces, CH-1015 Lausanne, Switzerland$$aShavaleev, Nail M.
000185450 700__ $$uCNR, Ist Sintesi Organ & Fotoreattivita, Mol Photosci Grp, I-40129 Bologna, Italy$$aMonti, Filippo
000185450 700__ $$0240189$$g148592$$uEcole Polytech Fed Lausanne, Lab Photon & Interfaces, CH-1015 Lausanne, Switzerland$$aScopelliti, Rosario
000185450 700__ $$aBaschieri, Andrea
000185450 700__ $$aSambri, Letizia
000185450 700__ $$uCNR, Ist Sintesi Organ & Fotoreattivita, Mol Photosci Grp, I-40129 Bologna, Italy$$aArmaroli, Nicola
000185450 700__ $$0240191$$g105292$$uEcole Polytech Fed Lausanne, Lab Photon & Interfaces, CH-1015 Lausanne, Switzerland$$aGraetzel, Michael
000185450 700__ $$aNazeeruddin, Mohammad K.$$uEcole Polytech Fed Lausanne, Lab Photon & Interfaces, CH-1015 Lausanne, Switzerland$$g105958$$0240422
000185450 773__ $$j32$$tOrganometallics$$k2$$q460-467
000185450 909C0 $$xU10101$$0252060$$pLPI
000185450 909CO $$pSB$$particle$$ooai:infoscience.tind.io:185450
000185450 917Z8 $$x105528
000185450 937__ $$aEPFL-ARTICLE-185450
000185450 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000185450 980__ $$aARTICLE