Raising the Bar in Aromatic Donor-Acceptor Interactions with Cyclic Trinuclear Gold(I) Complexes as Strong π-Donors.

Aromatic donor-acceptor interactions are of high importance in supramolecular chemistry, materials science and biology. Compared to other noncovalent interactions, such as hydrogen bonding, the binding is often weak. Here we show that strong donor-acceptor interactions between planar aromatics with binding free energies down to -10.1 kcal mol-1 and association constants of up to 2.34 × 107 L mol-1 for 1:1 complexes can be realized using cyclic trinuclear complexes of gold(I) with pyridinate, imidazolate, or carbeniate ligands. Data were obtained through NMR and UV/vis absorption spectroscopic studies and supported by quantum chemical calculations for a variety of acceptors. By using a specifically designed bridged naphthalene diimide-based acceptor with only one binding site, we furthermore show that a 1:2 (donor:acceptor) binding model is best suited to quantify the donor and acceptor/complex equilibrium. Scanning electron microscopy on selected donor-acceptor pairs shows crystalline supramolecular assemblies. We anticipate this study to be relevant for the future design of supramolecular systems and chemical sensors and the determination of binding energies between planar donors and acceptors.

Donor-acceptor interactions between cyclic trinuclear pyridinate gold(i)-complexes and electron-poor guests: nature and energetics of guest-binding and templating on graphite.

Donor-acceptor-type interactions between π-electron systems are of high relevance in the design of chemical sensors. Due to their electron-rich nature, cyclic trinuclear complexes (CTCs) of gold(i) are ideal receptor sites for electron-deficient aromatic analytes. Scanning tunneling microscopy provided insight into the structures of two-dimensional crystals of pyridinate gold CTCs that form on a graphite template at the solid/liquid interface. One polymorph thereof - in turn - templated the on-top co-adsorption of π-acidic pyrazolate CTCs as electron-poor guests up to a certain threshold. From NMR titration experiments, we quantified free energies of -6.1 to -7.5 kcal mol-1 for the binding between pyridinate gold(i) CTCs and π-acidic pyrazolate CTCs. Quantum chemical calculations revealed that these interactions are largely dominated by London dispersion. These results give a more detailed insight into a rational design of sensitive CNT- or graphene-based sensors for π-acidic analytes, such as electron-deficient aromatics.