A MOF-253 supported active Ru carbonyl complex (MOF-253-Ru(CO)2Cl2) was constructed for photocatalytic CO2 reduction under visible light irradiation. Its performance can be further improved by immobilization as a photosensitizer. This study highlights the great potential of using MOFs as a solid ligand and platform for the assembly of a complicated catalytic system.

Cationic Au4Ag2 heterohexanuclear aromatic acetylides cluster complexes supported by bis(2‐diphenylphosphinoethyl)phenylphosphine (dpep) are prepared. The Au4Ag2 cluster structure originating from the combination of one anionic [Au(C≡CR)2]− with one cationic [Au3Ag2(dpep)2(C≡CR)2]3+ through the formation of Ag−acetylide η2‐bonds is highly stabilized by Au–Ag and Au–Au contacts. The Au4Ag2 alkynyl cluster complexes are moderately phosphorescent in the fluid CH2Cl2 solution, but exhibit highly intense phosphorescent emission in solid state and film. As revealed by theoretical computational studies, the phosphorescence is ascribable to significant 3[π (aromatic acetylide) → s/p (Au)] 3LMCT parentage with a noticeable Au4Ag2 cluster centered 3[d → s/p] triplet state. Taking advantage of mCP and OXD‐7 as a mixed host with 20 wt% dopant of phosphorescent Au4Ag2 cluster complex in the emitting layer, solution‐processed organic light‐emitting diodes (OLEDs) exhibit highly efficient electrophosphorescence with the maximum current, power, and external quantum efficiencies of 24.1 cd A−1, 11.6 lm W−1, and 7.0%, respectively. Introducing copper(I) thiocyanate (CuSCN) as a hole‐transporting layer onto the PEDOT:PSS hole‐injecting layer through the orthogonal solution process induces an obvious improvement of the device performance with lower turn‐on voltage and higher electroluminescent efficiency.