Ruthenium (II) Complexes Bearing Heteroleptic Terpyridine Ligands: Synthesis, Photophysics and Solar Energy Conversion

Abstract

Heteroleptic ruthenium (II) complexes featuring donor functionalized phenyl‐terpyridine (ph‐tpy) and a monocarboxylic‐(ph‐tpy)/(tpy) are synthesized and characterized. Reactions of ruthenium (II) precursors at 80 °C favored heteroleptic complexes formation over the homoleptic side products. Visible light excitation of these complexes resulted in the metal‐to‐ligand charge transfer (MLCT) transitions. The inter‐planar torsional angle between the atoms of donor functionalized phenyl ring and the central pyridine (py) of the tpy core strongly influences visible light absorption and photovoltaic properties. The lower inter‐ring py‐ph torsion in the acceptor end of the MLCT structures and its increase in the oxidized doublets could prevent the back electron transfer. The ruthenium atom and the acceptor functionalized tpy host the triplet‐MLCT spin density. Ambient temperature excited‐state decay followed the energy gap law and occurred in the order of a few nanoseconds. Herein, we evaluate the photosensitizing ability of these complexes via a combined experimental and computational approach.

Understanding the role of inorganic carrier transport layer materials and interfaces in emerging perovskite solar cells

“…[76][77][78] The wide adaptability of TiO 2 as photoanodes in DSSCs has promoted it as an interesting ETL material in PSCs. 79,80 TiO 2 , which is an n-type wide bandgap semiconductor (i.e., E g = 3.2 eV with CB edge level at À4.2 eV and VB edge level at À7.0 eV), is one of the most transparent materials to visible light and offers electronically favourable band edge alignment with most of the known perovskite absorbers. Usually, a compact TiO 2 film is used as the hole-blocking layer in PSCs.…”

DFT calculation for graphene/hexagonal-boron-nitride nanoisland applicate in photonic device

“…Where ∅(inje.) and nc are electron injection efficiency and electron collect efficiency, respectively [17].…”

Ruthenium Complexes Bearing Bis‐N‐heterocyclic Carbene Donors in TiO2 Sensitization for Dye‐Sensitized Solar Cells

“…Preparation of [Ru(tpy 4'À COOMe )(C^C)(NCCH 3 )][PF 6 ] 2 [2] The general procedure starting from [(η 6 -p cymene)-Ru(C^C)(I)][I] (0.150 g, 0.22 mmol), tpy 4'À COOMe (0.070 g, 0.24 mmol), silver nitrate (0.041 g, 0.24 mmol) and dry-degassed acetonitrile (25 mL) afforded [2] as hygroscopic red solids (0.068 g, 0.075 mmol). Yield: 34.31 %.…”

“…[10] Subsequently, the reaction of (I) with ([(η 6 -p cymene)-Ru(Cl 2 )] 2 under refluxing acetonitrile afforded ([(η 6 -p cymene)-Ru(C^C)(I)][I]. [6c] Further, its reaction with ester-functionalized terpyridine ligands ( R tpy; R = 4'-PhCOOCH 3 or 4'-COOCH 3 ) in acetonitrile rendered the substitution of p-cymene by R tpy to afford [1] and [2], respectively.…”

“…Subsequent reactions of [1] or [2] with methyl isonicotinate in refluxing dichloromethane gave [3] or [4] as hygroscopic red solids. On the other hand, the reaction of [1] or [2] with potassium thiocyanate in dimethylformamide at 100 °C gave the À NCS-bound complexes of [5] and [6], respectively.…”