Dedicated to Professor Xiaozeng You on the occasion of his 80th birthdayIcosahedral closo-carboranes including 1,2-, 1,7-, and 1,12-C 2 B 10 H 12 (that is, o-, m-, and p-carborane) have been intensively investigated for decades owing to their unique 3D pseudo aromatic geometric structures and push-pull electronic properties.[1] Recently, more attention has been paid to optoelectronic properties of carborane-based materials.[2] However, the effects of carborane cage itself on photophysical properties of materials still need further investigation, especially for o-carborane derivatives, which possess an unusual C À C bond (in the range of 1.62-2.15 for the bond distance) [3] and usually quench luminescence.Better understanding of this phenomenon is important to guide further molecular design of carborane-containing luminescent materials. On the other hand, nido-carboranefunctionalized luminescent compounds are less studied [4] in comparison to closo-carborane-based derivatives, despite hydrophilic nido-carborane derivatives being promising candidates for biological applications such as in bioimaging.In the last decade, phosphorescent iridium(III) complexes have been widely used in organic light-emitting diodes (OLEDs), [5] chemosensors, [6] and bioimaging [7] owing to their stable chemical structure, high luminescent efficiency, and tunable excitation and emission wavelength over the whole visible range. However, few carborane-based phosphorescent iridium(III) complexes have been reported. [8] It is anticipated that introduction of carborane cages into phosphorescent iridium(III) complexes may further improve the photophysical properties of these complexes and allow better understanding the roles of carborane groups. As such, we chose the well-studied homoleptic triply cyclometalated phosphorescent iridium(III) complexes [Ir(ppy) 3 ][9] (ppy = 2-phenylpyridine) as control compounds and synthesized a series of facial and meridional iridium(III) complexes containing o-, m-, or p-carboranyl units in the cyclometalated C^N ligand, denoted as fac-o, fac-m, and fac-p for facial complexes and mer-o, mer-m, and mer-p for meridional complexes (Scheme 1). The results demonstrate that introduction of m-and p-carborane cages can improve phosphorescence efficiency (F P ) of both facial and meridional structures. The luminescent efficiency of the o-carborane derivative fac-o exhibits solvent-or media-dependence, which is closely related to dielectric constant (e) of media as the specific C À C bond of o-carborane is involved in excited state and highly sensible to media. A new phosphorescent iridium-(III) complex containing nido-o-carborane cages has been prepared as well, which possesses stable chemical structure, excellent water solubility, high phosphorescence efficiency (absolute F P = 0.36 in aqueous solution), and a long emission lifetime, thus has been successfully applied in cellular bioimaging.All of the carborane-functionalized cyclometalated ligands (R-ppy) were prepared through an efficient SuzukiMiyaura cross-co...