Brightly luminescent Pt(II) pincer complexes with a sterically demanding carboranyl-phenylpyridine ligand: a new material class for diverse optoelectronic applications.

A series of three Pt(II) complexes with a doubly cyclometalating terdentate ligand L1, L1H2 = 3,6-bis(p-anizolyl)-2-carboranyl-pyridine, and diethyl sulfide (1), triphenylphosphine (2), and t-butylisonitrile (3) as ancillary ligands were synthesized. X-ray diffraction studies of 1 and 2 show a coordination of the L1 ligand in a C-N-C mode in which the bulky and rigid o-carborane fragment is cyclometalated via a C atom. Importantly, no close intermolecular Pt-Pt contacts occur with this ligand type.

2,2'-Bipyridinyl carboranes as B,N,N-ligands in cyclometallated complexes of platinum(II).

Novel B,N,N-cyclometallated Pt(II) complexes of 2,2'-bipyridin-6-yl carboranes exhibit absorption and emission similar to relative Pt(II) complexes of aromatic C,N,N-ligands: the same transitions but lower intensities. DFT calculations suggest the former emits from the (3)MLCT state while for the latter the mixed (3)ICT-MLCT transitions should be considered.

Phosphorescence vs fluorescence in cyclometalated platinum(II) and iridium(III) complexes of (oligo)thienylpyridines.

Two newly prepared oligothienylpyridines, 5-(2-pyridyl)-5'-dodecyl-2,2'-bithiophene, HL(2), and 5-(2-pyridyl)-5''-dodecyl-2,2':5',2''-ter-thiophene, HL(3), bind to platinum(II) and iridium(III) as N∧C-coordinating ligands, cyclometallating at position C(4) in the thiophene ring adjacent to the pyridine, leaving a chain of either one or two pendent thiophenes. The synthesis of complexes of the form [PtL(n)(acac)] and [Ir(L(n))(2)(acac)] (n = 2 or 3) is described. The absorption and luminescence properties of these four new complexes are compared with the behavior of the known complexes [PtL(1)(acac)] and [Ir(L(1))(2)(acac)] {HL(1) = 2-(2-thienyl)pyridine}, and the profound differences in behavior are interpreted with the aid of time-dependent density functional theory (TD-DFT) calculations.

Emissive metallomesogens based on 2-phenylpyridine complexes of iridium(III).

Preparation of Ir(III) complexes using anisotropic 2,5-di(4-alkoxyphenyl)pyridine ligands leads to emissive, liquid-crystalline complexes containing bound Cl and dimethyl sulfoxide. Using analogous poly(alkoxy) ligands allows the preparation of bis(2-phenylpyridine)iridium(III) acac complexes, which are also mesomorphic. The observation of liquid crystallinity in octahedral complexes of this type is without precedent.