6,6′-Ditriphenylamine-2,2′-bipyridine: Coordination Chemistry and Electrochemical and Photophysical Properties

Abstract

A 2,2′-bipyridine with bulky triphenylamine substituents in the 6 and 6′ positions of the ligand (6,6′-ditriphenylamine-2,2′-bipyridine, 6,6′-diTPAbpy) was generated. Despite the steric bulk, the ligand readily formed bis­(homoleptic) complexes with copper­(I) and silver­(I) ions. Unfortunately, efforts to use the 6,6′-diTPAbpy system to generate heteroleptic [Cu­(6,6′-diTPAbpy)­(bpy)]+ complexes were unsuccessful with only the [Cu­(6,6′-diTPAbpy)2]­(PF6) complex observed. The 6,6′-diTPAbpy ligand could also be reacted with 6-coordinate metal ions that featured small ancillary ligands, namely, the [Re­(CO)3Cl] and [Ru­(CO)2Cl2] fragments. While the complexes could be formed in good yields, the steric bulk of the TPA units does alter the coordination geometry. This is most readily seen in the [(6,6′-diTPAbpy)­Re­(CO)3Cl] complex where the Re­(I) ion is forced to sit 23° out of the plane formed by the bpy unit. The electrochemical and photophysical properties of the family of compounds were also examined. 6,6′-diTPAbpy exhibits a strong ILCT absorption band (356 nm, 50 mM–1 cm–1) which displays a small increase in intensity for the homoleptic complexes ([Cu­(6,6′-diTPAbpy)2]+; 353 nm, 72 mM–1 cm–1, [Ag­(6,6′-diTPAbpy)2]+; 353 nm, 75 mM–1 cm–1), despite containing 2 equiv of the ligand, attributed to an increased dihedral angle between the TPA and bpy moieties. For the 6-coordinate complexes the ILCT band is further decreased in intensity and overlaps with MLCT bands, consistent with a further increased TPA-bpy dihedral angle. Emission from the 1ILCT state is observed at 436 nm (τ = 4.4 ns) for 6,6′-diTPAbpy and does not shift for the Cu, Ag, and Re complexes, although an additional 3MLCT emission is observed for [Re­(6,6′-diTPAbpy)­(CO)3Cl] (640 nm, τ = 13.8 ns). No emission was observed for [Ru­(6,6′-diTPAbpy)­(CO)2Cl2]. Transient absorption measurements revealed the population of a 3ILCT state for the Cu and Ag complexes (τ = 80 ns). All assignments were supported by TD-DFT calculations and resonance Raman spectroscopic measurements.

Investigation of the Geometric and Spectroscopic Properties of Four Twisted Triphenylpyridinium Donor–Acceptor Dyes

“…Resonance Raman spectra were collected by methods previously used . A laser excitation was focused on a spinning NMR tube in a 135° backscattering geometry.…”

“…Each of these studies suggests that external environment and geometrical constraints have a large effect on the electronic properties of cationic triphenylpyridinium acceptor-based dyes. Triphenylamine and carbazole groups are common aromatic donor moieties in donor–acceptor dyes, utilized for their good electron-donating ability and electronic tuning. ,,,− Herein, we report the spectroscopic properties of four TPP -based donor–acceptor dyes with four respective donor groups (Figure ) and the importance of their geometry on their electronic behavior. Each donor was substituted onto the pyridinium nitrogen: 9-phenylcarbazole (in TPP-Ph-Cbz ), triphenylamine (in TPP-TPA ), and two carbazole based donors bound at the C 3 position, consisting of N -phenyl (in TPP-Cbz-Ph ) and N -ethyl (in TPP-Cbz-Et ) auxiliary donors, respectively.…”

“…Resonance Raman spectra were collected by methods previously used. 30 A laser excitation was focused on a spinning NMR tube in a 135°b ackscattering geometry. Solid-state diodes provided excitation wavelengths of 355, 457, 491, and 515 nm (Cobolt, Sweden); 375 and 448 nm (CrystaLaser, USA); and 405 nm (Ondax, USA).…”