Calculated Optoelectronic Properties of Ruthenium Tris-bipyridine Dyes Containing Oligophenyleneethynylene Rigid Rod Linkers in Different Chemical Environments

Abstract

Ruthenium tris-bipyridine dyes containing oligophenyleneethynylene (OPE) rigid rod linker groups ([Ru(bpy)3]2+, [Ru(bpy)2bpy-E-Ipa]2+, [Ru(bpy)2bpy-E-Ph-E-Ipa]2+, and [Ru(bpy)2bpy-E-Bco-E-Ipa]2+, where bpy = 2,2'-bipyridine, E = ethynylene, Ph = p-phenylene, Bco = bicyclo[2.2.2]octylene, and Ipa = isophthalic acid) have been investigated using DFT and TD-DFT calculations to elucidate the influence of the rigid rod on their optoelectronic properties. Experimentally observed differences in the optical absorption for the different complexes are discussed on the basis of TD-DFT simulated absorption spectra. A comparison of the calculated optoelectronic properties of [Ru(bpy)2bpy-E-Ph-E-Ipa]2+ in different chemical environments, that is, in different solvents and with or without counter ions, suggests that both the absorption spectra and the redox properties of the dyes with OPE rods are sensitive to the environment. The calculations show that spurious low-energy charge-transfer excitations present in the TD-DFT calculations of the extended systems in vacuum are removed when the environment is included in the calculations.

Quantum-chemical calculations of dye-sensitized semiconductor nanocrystals

“…We have recently compared results from calculations of a series of ruthenium tris-bipyridine dyes carrying so-called rigid rods in different chemical environments. 12 This is illustrated in Fig. 6 for [Ru(bpy) 2 bpy-E-Ph-E-Ipa] +2 (bpy = 2,2'-bipyridine, E = ethynylene, Ph = p-phenylene, Ipa = isophtalic acid) in gas phase and in a polarisable continuum model (PCM) treatment of acetonitrile.…”

Virtual Eyes Designed for Quantitative Spectroscopy of Inorganic Complexes: Vibronic Signatures in the Phosphorescence Spectra of Terpyridine Derivatives

“…9 In particular, polypyridine Ruthenium complexes have been extensively studied from both theoretical and experimental points of views and remain preferential targets due to their strong luminescent properties and their ability to be entrapped in many different devices. [10][11][12][13][14][15][16] However, from a pure experimental point of view, it remains difficult to fully characterize those compounds with a single technique, and it is often necessary to deal with a multi-spectroscopic approach. In this context, quantum mechanical computations by methods rooted into the density functional theory (DFT) and its time dependent extension (TD-DFT) are increasingly used to obtain complementary electronic and vibrational information for medium to large-size systems thanks to terrific improvements of hardware and software.…”

A review on spectral converting nanomaterials as a photoanode layer in dye‐sensitized solar cells with implementation in energy storage devices

“…It is observed that photoanode layer of Eu‐doped TiO 2 enhances efficiency as compared to undoped TiO 2 and this important property of doping plays an important role in altering the material for DSSCs to exhibit better performance . Figure represents the fabrication of DSSCs with Eu‐doped TiO 2 as photoanode, distinctly showing dye absorption, electrolyte reduction and oxidation, electron‐injection and conduction process Recently, Kharel et al stated that alike RE metals, RE oxides (REO‐ Er 2 O 3 and Nd 2 O 3 ) doped into TiO 2 also show improvement in the photoconversion efficiency of DSSCs .…”