Structural and Photochemical Properties of Zn(II) Phenanthroline-Derived Complexes: From Mononuclear to Bimetallic and Circular-Trimetallic Helicates.

In the design of self-assembled compounds, small variations in the linkers connecting the coordinating moieties can produce large differences in the obtained structures. Here, we report three novel zinc(II) complexes with phenanthroline-derived ligands as building blocks (L1-L3): A mononuclear complex, a bimetallic helicate, and a trimetallic circular helicate. The even-number spacer in L2 promotes the formation of a bimetallic helicate stabilized by π-π interactions of adjacent phenanthrolines. The addition of an extra methylene in L3 increases the distance between where the phenanthrolines can stack, and CH-π noncovalent interactions give stability to the circular helicate. When irradiated at 308 nm in acetonitrile, long-lived excited states are formed with all three complexes, which are able to participate in oxidation of 2-propanol and in reduction of methylviologen, MV2+. While the overall behavior of the three complexes is similar, the bimetallic helicate is able to form a ground-state adduct with MV2+, while the trimer reaches the excited state to form an exciplex with MV2+.

Structural diversity in Cu(i) complexes of the PNP ligand: from pincer to binuclear coordination modes and their effects upon the electrochemical and photophysical properties.

A set of new copper(i) complexes is synthesized and characterized using a labile PNP pincer ligand (PNP = N,N'-bis(diphenylphosphine)-2,6-diaminopyridine). A homoleptic Cu(i) complex [Cu(PNP-κP1:κN1)2]+, (1), was prepared, and taking advantage of the uncoordinated phosphorus atoms in (1), reaction with a second Cu(i) atom bearing secondary ligands (PPh3, phen or dmp) allows the formation of new complexes: a bimetallic helicate [Cu(PNP)2(phen)]2+, (2), a mononuclear pincer complex [CuI(PNP)(PPh3)]+, (3), and a heteroleptic complex [CuI(PNP)(dmp)]+, (4). All complexes were characterized by X-ray crystallography, NMR (VT-NMR for (1) and (4)), cyclic-voltammetry, and steady-state and time-resolved luminescence spectroscopy. The fluxional behavior in (1) was studied by 31P VT-NMR, where an Ea value of 47.42 kJ mol-1 was calculated for the intramolecular alternating coordination of -PPh2 moieties in PNP to the metal atom. This set of compounds reveals the versatility of the PNP ligand when added to the coordinating properties of Cu(i). The four complexes exhibit emission in solution and complexes (2)-(4) display intense luminescence in the solid state. The oscillographic traces showing the decay of the luminescence were fitted to biexponential functions with time constants: 8.0 µs > τem,1 > 0.37 µs and 50 µs >τem, 2 > 2.2 µs for complexes (2), (3) and (4), respectively. Radiative relaxation is associated with electronic transitions in both the ligand PNP and metal-to-ligand charge transfer (MLCT).