Herein we describe the synthesis and characterization of the first platinum(IV) metal−organic cage [(Me 3 Pt IV ) 8 (byp) 12 ](OTf) 8 ( 2), in which the organometallic moieties trimethylplatinum(IV) (PtMe 3 ) occupied the corners of a cubane structure and 4,4′-bipyridine ligands used as linkers. The first-principles density functional theory calculations showed that the highest occupied molecular orbitals were localized on the PtMe 3 moieties, while the lowest unoccupied molecular orbitals were distributed on the organic linkers.

Naphthalimide derivatives provide highly versatile self-assembled systems and aggregated forms with fascinating emission properties that make them potential candidates for many applications such as bioimaging and sensing. Although various aggregated species of naphthalimide derivatives have been well documented, little is known about the correlation between their structure and photophysical properties. Here the preparation of a series of tetrameric naphthalimide molecules in which naphthalimide units are linked by bis-N-heterocyclic carbene complexes of coinage metals is described. An in-depth structural investigation into these tetramers has been carried out in solution and the solid state using spectroscopic methods, X-ray crystallography, and computational methods. The experimental and calculated data indicate that the magnitude of the intramolecular interchromophoric π-interactions increases either by an increase in the metal ionic radius or on going from the solid to the solution state. These tetrameric naphthalimide compounds show intramolecular excimeric emissions in the solid and solution phases. However, the quantum yield efficiencies of these excimeric emissions show a trend similar to that for the intramolecular π-interactions either by going from the solution to the solid state or with an increase in the metal ionic radius. Surprisingly, the amine derivative analogues of the silver­(I) compound showed an unusual increase in the emission quantum yield efficiency to 92% in solution due to intramolecular hydrogen bonds between amine substituents on adjacent naphthalimde units.