title: Luminescent organoplatinum(II) complexes with functionalized cyclometalated C^N^C ligands: structures, photophysical properties, and material applications.
abstract: A series of [(R'-C^N^C-R'')Pt(L)] complexes with doubly deprotonated cyclometalated R'-C^N^C-R'' ligands (R'-C^N^C-R''=2,6-diphenylpyridine derivatives) functionalized with carbazole, fluorene, or thiophene unit(s) have been synthesized and their photophysical properties studied. The X-ray crystal structures reveal extensive intermolecular π···π and C-H···π interactions between the cyclometalated C^N^C ligands. Compared to previously reported cyclometalated platinum(II) complexes [(C^N^C)Pt(L)], which are non-emissive in solution at room temperature, the carbazole-, fluorene- and thiophene-functionalized [(R'-C^N^C-R'')Pt(L)] (L=DMSO 1-9, C≡N-Ar, 1a-9a) complexes are emissive in solution at room temperature with λ(max) at 564-619 nm and Φ=0.02-0.26. The emissions of the [(R'-C^N^C-R'')Pt(L)] complexes are attributed to electronic excited states with mixed (3)MLCT and (3)IL character. The carbazole/fluorene/thiophene unit(s) allow the tuning of the electronic properties of the [(R'-C^N^C-R'')Pt] moiety, with the emission maxima in a range of 564-619 nm. These are the first examples of organoplatinum(II) complexes bearing doubly deprotonated cyclometalated C^N^C ligands that are emissive in solution at room temperature. In non-degassed DMSO, the emission intensities of 6a-9a are enhanced upon exposure to ambient light. This phenomenon is caused by reacting photogenerated (1)O(2) with a DMSO molecule to form dimethyl sulfone, leading to the removal of dissolved oxygen in solution. Self-assembled nanowires and nanorods are obtained from precipitation of 3a in THF/H(2)O and 8a in DMSO/Et(2)O, respectively. The [(R'-C^N^C-R'')Pt(L)] complexes are soluble in common organic solvents with a high thermal stability (>300 °C), rendering them as phosphorescent dopants for organic light-emitting diode (OLEDs) applications. Red OLEDs with CIE coordinates of (0.65±0.01, 0.35±0.01) were fabricated from 7a or 8a. A maximum external efficiency (η(Ext)) of 12.6% was obtained for the device using 8a as emitter.
authors.affiliation: Department of Chemistry, State Key Laboratory of Synthetic Chemistry, Institute of Molecular Functional Materials, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.
authors.forename: Steven C F
authors.initials: SC
authors.lastname: Kui
authors.forename: Faan-Fung
authors.initials: FF
authors.lastname: Hung
authors.forename: Shiu-Lun
authors.initials: SL
authors.lastname: Lai
authors.forename: Mai-Yan
authors.initials: MY
authors.lastname: Yuen
authors.forename: Chi-Chung
authors.initials: CC
authors.lastname: Kwok
authors.forename: Kam-Hung
authors.initials: KH
authors.lastname: Low
authors.forename: Stephen Sin-Yin
authors.initials: SS
authors.lastname: Chui
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Che