We report a combine
d experimental an
d theoretical stu
dy on cationic Ir(III) complexes for OLED applications an
ddescribe a strategy to tune the phosphorescence wavelength an
d to enhance the emission quantum yiel
ds for thisclass of compoun
ds. This is achieve
d by mo
dulating the electronic structure an
d the excite
d states of the complexesby selective ligan
d functionalization. In particular, we report the synthesis, electrochemical characterization, an
dphotophysical properties of a new cationic Ir(III) complex, [Ir(2,4-
difluorophenylpyri
dine)
2(4,4'-
dimethylamino-2,2'-bipyri
dine)](PF
6) (N969), an
d compare the results with those reporte
d for the analogous [Ir(2-phenylpyri
dine)
2(4,4'-
dimethylamino-2,2'-bipyri
dine)](PF
6) (N926) an
d for the prototype [Ir(2-phenylpyri
dine)
2(4,4'-
tert-butyl-2,2'-bipyri
dine)](PF
6) complex, hereafter labele
d N925. The three complexes allow us to explore the (C
d.gif">N) an
d (N
d.gif">N) ligan
dfunctionalization: consi
dering N925 as a reference, we investigate in N926 the effect of electron-releasing substituentson the bipyri
dine ligan
d, while in N969, we investigate the combine
d effect of electron-releasing substituents on thebipyri
dine ligan
d an
d the effect of electron-with
drawing substituents on the phenylpyri
dine ligan
ds. For N969 weobtain blue-green emission at 463 nm with unprece
dente
d high quantum yiel
d of 85% in acetonitrile solution atroom temperature. To gain insight into the factors responsible for the emission color change an
d the
differentquantum yiel
ds, we perform DFT an
d TDDFT calculations on the groun
d an
d excite
d states of the three complexes,characterizing the excite
d-state geometries an
d inclu
ding solvation effects on the calculation of the excite
d states.This computational proce
dure allows us to provi
de a
detaile
d assignment of the excite
d states involve
d in theabsorption an
d emission processes an
d to rationalize the factors
determining the efficiency of ra
diative an
dnonra
diative
deactivation pathways in the investigate
d complexes. This work represents an example of electronicstructure-
driven tuning of the excite
d-state properties, thus opening the way to a combine
d theoretical an
d experimentalstrategy for the
design of new iri
dium(III) phosphors with specific target characteristics.