Mononuclear Ru(II) PolyPyridyl Water Oxidation Catalysts Decorated with Perfluoroalkyl C₈H₁₇‐Tag Bearing Chains

Abstract

A set of novel polypyridyl Ru(II) complexes 1-7, decorated with one, two or three C 8 F 17 tags have been synthesized and characterized by NMR, UV/Vis spectroscopy and, in the case of series of complexes 1-3, 5 and 7 by X-ray diffraction on single crystals. Solid state structures of 3, 5 and 7 were also subjected to computational DFT study in order to gain insights [a] 4463 into the effect of a different number of perfluorinated tags on their stability in the solid-state. The complexes are stable in solution under strongly oxidative conditions, do keep catalytic activity in their aquo forms (1′-7′) comparing well with parent complex 8′, and their amphiphilic nature could allow for their incorporation in fluorous media and interfaces.by the classic bipy/terpy core but are additionally decorated with one, two or three C 8 F 17 fluorinated pendants. Scheme 1. Molecular formulae of the Ru(II) complexes 1-7 and of the model 8 used as reference.4464 Scheme 2. Synthetic procedure for complexes 1-7 and intermediates 9a-d and 10a-d.

A Bispidine Based CuII/ZnII Heterobimetallic Coordination Polymer

“…The packing is directed by two main elements, which are the chloride counterion, and the 1,2‐DCB solvent molecules entrapped within the lattice. The former, at 7.643 Å distance from the closest Mn II center, directs the assembly around itself of four complexes (Figure 1c) via several CH arom ⋅⋅⋅Cl − hydrogen bond (HB) interactions (C⋅⋅⋅Cl distances in the 3.467–3.653 Å range) with pyridine rings, and via one OH⋅⋅⋅Cl − HB with the gem‐diol unit (O⋅⋅⋅Cl distance of 3.029 Å), similar to what is observed in other examples of second sphere coordination in polypyridyl metal complexes [22] . The solvent has also an important role in the final structure, adopting two different locations, being disordered in one of them, and displaying no evidence of any strong specific interaction with neither metalloligands nor counteranions.…”

“…The packing is directed by two main elements, which are the chloride counterion, and the 1,2-DCB solvent molecules entrapped within the lattice. The former, at 7.643 Å distance from the closest Mn II center, directs the assembly around itself of four complexes (Figure 1c [22] The solvent has also an important role in the final structure, adopting two different locations, being disordered in one of them, and displaying no evidence of any strong specific interaction with neither metalloligands nor counteranions. Interestingly, it resides within a channeled framework which, if virtually evacuated, would possess void space corresponding to 29.3 % of the total unit cell volume (Figure 1d).…”

Crystal engineering strategies towards halogen-bonded metal–organic multi-component solids: salts, cocrystals and salt cocrystals

“…17e). 125 Alongside the aforementioned 'classical' complex cations, strategy 3a was also extensively employed in the preparation of halogen-bonded cocrystals of halogenides of alkali and alkaline earth metal complexes with (neutral) macrocyclic ligands (Fig. 18).…”

Immobilising molecular Ru complexes on a protective ultrathin oxide layer of p-Si electrodes towards photoelectrochemical CO2 reduction

“…The average Ru-N terpy distance of 2.040 (3) Å is within the range of previously reported examples (range 1.958-2.083 Å), while the average Ru-N bipy 2.086 (8) Å lengths are slightly elongated (range 2.019-2.085 Å). [49][50][51] Unfortunately, very low intensity data were obtained from single crystals of (2), which did not allow for the structure to be discussed beyond connectivity information. Further details for both structures are provided in the ESI.…”