Complementary coordination of two predesigned 2,2':6',2″-terpyridine-based ligands to a Zn ion led to the exclusive formation of a heteroleptic bis(terpyridine) complex under ambient conditions. This highly self-selective process was facilitated by 9-anthracenyl substituents at the 6,6″-positions of a terpyridine, which not only decelerated the formation rate of its homoleptic complex, but also provided π-stacking stabilization in the heteroleptic complex. Facile construction of metallo-supramolecular poly(3-hexylthiophene) (P3HT)-block-poly(ethylene oxide) (PEO) diblock copolymers was realized using the complementary ligand pair. The morphological studies of the amphiphilic block copolymers in solution were conducted by atomic force microscopy and transmission electron microscopy, indicating that the self-assembled core-shell morphology such as spherical and fibrillar nanostructures could be controlled by adjusting the rod-coil block ratios. The heteroleptic complexes residing at the junction between two polymer blocks could be readily dissociated by EDTA to afford the unshelled P3HT nanofiber networks, and restored by treatment of bifunctional Zn-terpyridine-capped PEO to redisperse the aggregates. The presented supramolecular methodology highlights the merits of complementary metal-ligand coordination, and offers a new approach to engineering nanostructures assembled from rod-coil block copolymers.

Predesigned complementary complexation of two 2,2':6',2″-terpyridine-based ligands was established by installing 2,6-dimethoxyphenyl substituents at the terpyridyl 6,6″-positions, which provided ancillary ion-dipole interactions in the coordination process and extra π-stacking stabilization in the resultant heteroleptic complex. The high-fidelity self-recognition ligation afforded facile access to the quantitative self-assembly of multicomponent triangle [Cd6L(3)3L(4)3] and ditrigon [Cd15L(3)6L(5)3] (that is, a hexagon with six 120° angles and two alternating edge lengths). It was found that the linear 6,6″-substituted ditopic motif (L(3)) would be directed by the ligand geometry of L(5) to selectively incorporate into the parallel homoleptic connections in the bilayered framework.

A series of metallo-supramolecular ring-in-ring structures was generated by assembling Cd(II) ions and the multivalent terpyridine ligands (L(1-3)) composed of one 60°-bent and two 120°-bent bis(terpyridine)s with varying alkyl linker lengths. The mechanistic study for the self-assembly process excluded an entropically templated pathway and showed that the intramolecularly complexed species is the key intermediate leading to ring-in-ring formation. The next-generation superstructure, a spiderweb, was produced in quantitative yield using the elongated decakis(terpyridine) ligand (L(5)).

Spontaneous formation of the heteroleptic cadmium(II) bis(terpyridine) complex under ambient conditions can be achieved by a combination of 6,6''-di(2,6-dimethoxylphenyl)-substituted and unsubstituted terpyridine-based ligands. Building on this dynamic heteroleptic complexation, diverse metallo-supramolecular macrocycles and cages were readily assembled in quantitative yields from the predesigned multicomponent systems. The complementary ligation reinforced self-recognition to facilitate the shape-dependent self-sorting of a four-component dynamic library into two well-defined parallelograms. In addition, the subtle lability difference between homoleptic and heteroleptic complexes led to the site-selective Cd -Zn transmetalation in the Sierpiński triangle. Facile construction of a dodecanuclear tetrahedral metallocage was also realized by using two self-recognizable tritopic building blocks. The photophysical study of the metallo-supramolecules assembled from the d metal ions revealed intense ligand-based photoluminescence in solution. The self-assembly strategy described here provides an efficient methodology for building pre-programmable, sophisticated supramolecular architectures furnished with photoactivity.

Three unsymmetrical, 60°-bended bisterpyridine ligands with varying phenylene spacer lengths have been synthesized via the Suzuki-Miyaura coupling reactions. Their self-assembly processes were found to be strongly dependent on the ligand geometry. Upon complexation with Zn(II) ions, only 2,4''-di(4'-terpyridinyl)-1,1':4',1''-terphenyl underwent self-selection to give a trinuclear metallomacrocycle with perfect heteroleptic connectivity and the other two afforded a mixture of constitutional isomers. The metallosupramolecular assemblies were characterized by NMR spectroscopy, electrospray mass spectrometry (ESI MS), and single-crystal X-ray diffraction. In particular, the identification of isomeric architecture was accomplished using tandem mass spectrometry (MS(2)) coupled with traveling wave ion mobility mass spectrometry (TWIM MS).