As an NNN-tridentate ligand, the 2,2':6',2"-terpyridine plays an important role in coordination chemistry. With three coordination sites and low LUMO, terpyridine and its derivatives are one of the typical Pincer ligand and/or non-innocent ligands in transition metal catalysis. Interesting catalytic reactivities have been obtained with these tpy-metal complexes targeting some challenging transformations, such as CC bond formation and hydrofunctionalization. On the other hand, terpyridine ligands can form "closed-shell" octahedral complexes, which provide a linear and stable linkage in supramolecular chemistry. Numerous supramolecular architectures have been achieved using modified terpyridine ligands including Sierpiński triangles, hexagonal gasket and supramolecular rosettes. This review presents a summary of recent progress regarding transition metal-terpyridine complexes with the focus on their applications in catalysis and supramolecular structure construction. Facile synthesis of terpyridine derivatives is also described. We hope this article can serve to provide some general perspectives of the terpyridine ligand and their applications in coordination chemistry.

A gold-catalyzed oxidative coupling of alkynes was developed as an efficient approach for the synthesis of challenging cyclic conjugated diynes (CCD). Compared to the classical copper-promoted oxidative coupling reaction of alkynes, this gold-catalyzed process exhibits a faster reaction rate due to the rapid reductive elimination from the Au(III) intermediate. This unique reactivity thus allowed a challenging diyne macrocyclization to take place in high efficiency. Condition screening revealed a [(n-Bu)4N]+[Cl-Au-Cl]− salt as the optimal pre-catalyst. Macrocycles with ring size between 13 to 28 atoms were prepared in moderate to good yields, which highlighted the broad substrate scope of this new strategy. Furthermore, the synthetic utilities of the cyclic conjugated diynes for copper-free click chemistry have been demonstrated, which showcased the potential application of this strategy in biological systems.

A donor/acceptor diazo activation strategy, processing via condensation using diazonium salts without the addition of any other catalysts or reagents, is reported. The diazenium intermediate was found to undergo cyclization to give indazoles in excellent yields. Alternatively, in the presence of nitriles, substituted 1,2,4-triazoles were obtained in good to excellent yields. This interesting diazenium route provides a new approach to achieve complex heterocycle synthesis under mild conditions.

Hexafluoroisopropanol (HFIP)-promoted disulfidation and diselenation of C−C unsaturated bonds is reported. Reactions of unactivated alkyne, alkene, and allene, respectively, with disulfides or diselenides in HFIP led to desired products in good to excellent yields (up to 96%). In contrast, other solvents, such as isopropanol and dichloroethane, could not promote the same reaction. This method revealed an example of HFIP-promoted transformations under the mild conditions, which greatly highlighted the unique reactivity of this special solvent.

The 1,2,3-triazole-imidazole derivatives (TA-IM) were prepared as fluorescent probes for silver ions detection. The design principle is the incorporation of an intramolecular H-bond between the imidazole and triazole moiety that enables a co-planar conformation to achieve fluorescence emission in UV-blue range. Screening of different metal ions revealed excellent binding affinity of this new class of compounds toward silver ions in aqueous solution. The novel probe provided ultrafast detection (< 30 s) even for a very low concentration of silver ions (at nM range) with good linear correlation, making it a practical sensor for detection of silver ions.