Abstract Homoleptic fac ‐substituted Ir(III) carbene complexes exhibit higher emission energy (in purple region) in comparison to their mer ‐counterparts, prohibiting them be employed fabrication of blue emissive organic light‐emitting diode (OLED) devices. Now, the design two distinctive CF 3 ‐functionalized purin‐8‐ylidene complexes, namely, m ‐ and f ‐CF ‐PhCF , from new motifs, 9‐(3‐( tert ...