Monovalent gold salts react with the ligand triphos in various diverging pathways, with outcomes predicated upon anion identity, gold-to-triphos ratio, and solvent system used. The first crystalline gold-triphos complex synthesized was a luminescent helicate first reported in 2001 (Shuh), with three gold centers and two aurophilic interactions. From that starting point, we have synthesized a number of contrasting complexes. For instance, the helicate can be dimerized through bridging by chloride or bromide with differing luminescent emission, but retaining its aurophilic interactions. In addition, these same starting materials have also been formed into a cationic box-like container [(Au6(triphos)4]6+ with identical stoichiometry to the helicate dimer. This box-like cation is capable of isolating several anionic species. These containers display luminescence without aurophilicity. Similarly, gold and triphos have been reacted to form non-emissive aurophilic polymers [triphos(AuX)3]n with chloride and bromide, as well as an emissive aurophilic dimer [triphos(AuI)3]2. Finally, they have also formed a complex displaying an unexpected combination of these properties, with two isolated bridging gold centers and two pairs of aurophilic interactions. In at least two cases, the application of pressure converts the box-like structure into the bridged helicate as shown by changes in the luminescence.

Simple building blocks into complex frameworks: The relationship between gold and triphos (PPh(CH2CH2PPh2)2).

2019 Spring National Meeting

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