Highly emissive tribenzotriquinacene-based double-rimed nanocube

The study of discrete nanosized cages has gone a long way to seek aesthetically appealing structures and to carry out functional applications.Although the construction of supramolecular cages via a bottom-up self-assembly process has been well developed,the sophisticated synthesis still remains a challenge.Here we report the design and assembly of a giant double-rimed nanocube Zn_(24)LH_(8),built with 8 tribenzotriquinacene as six-connected vertices and 24<tpy-Zn^(2+)-tpy>(tpy=terpyridine)connectivities serving as the edges.From the single-crystal structure of tribenzotriquinacene-based ligand LH,the bowl-shaped ligand defines a suitable rigid platform for the spatially well-defined attachment of three sets of parallel vertices,which promotes the quantitative formation of the desired three-dimensional(3D)double-rimed cubic architectures.The formed nanocube Zn_(24)LH_(8)possesses molecular weight up to 25.6 kDa and side length 5.3 nm.Remarkably,the Zn_(24)LH_(8)exhibits strong cyan light emission with high luminescence quantum yields in solution and in the solid state based on the inherent cage-confinement induced emission enhancement.By adding orange-emissive Rhodamine B,emission tuning experiments were achieved including white light emission.This work presents a new system for the imitation of complex assemblies and provides a promising candidate for emissive materials.

Trefoil-shaped metallacycle and metallacage via heteroleptic self-assembly

Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional(2D)and three-dimensional(3D)supramolecules,but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge.Here we report two discrete trefoil-shaped metallacycle S1 and metallacage s2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands.The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic'Mitsubishi motif.The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2.The formed metallacage S2 possesses a molecular weight up to 36 kDa,diameter 6.6 nm and height 3.0 nm.All supramolecular coordination complexes were fully characterized by NMR spectroscopy(^(1)H NMR,2D COSY,2D NOESY,2D DOSY),high-resolution electrospray ionization mass sectrometry ESI-MS.ESI-TWIM-MS,TEM and AFM.