The influence of molecular mobility on the properties of networks of gold nanoparticles and organic ligands

We prepare and investigate two-dimensional (2D) single-layer arrays and multilayered networks of gold nanoparticles derivatized with conjugated hetero-aromatic molecules, i.e., S-(4-{[2,6-bipyrazol-1-yl)pyrid-4-yl]ethynyl}phenyl)thiolate (herein S-BPP), as capping ligands. These structures are fabricated by a combination of self-assembly and microcontact printing techniques, and are characterized by electron microscopy, UV–visible spectroscopy and Raman spectroscopy. Selective binding of the S-BPP molecules to the gold nanoparticles through Au–S bonds is found, with no evidence for the formation of N–Au bonds between the pyridine or pyrazole groups of BPP and the gold surface. Subtle, but significant shifts with temperature of specific Raman S-BPP modes are also observed. We attribute these to dynamic changes in the orientation and/or increased mobility of the molecules on the gold nanoparticle facets. As for their conductance, the temperature-dependence for S-BPP networks differs significantly from standard alkanethiol-capped networks, especially above 220 K. Relating the latter two observations, we propose that dynamic changes in the molecular layers effectively lower the molecular tunnel barrier for BPP-based arrays at higher temperatures

Shorter alkyl chains enhance molecular diffusion and electron transfer kinetics between photosensitisers and catalysts in CO2-reducing photocatalytic liposomes

Covalent functionalisation with alkyl tails is a common method for supporting molecular catalysts and photosensitisers onto lipid bilayers, but the influence of the alkyl chain length on the photocatalytic performances of the resulting liposomes is not well understood. In this work, we first prepared a series of rhenium-based CO2-reduction catalysts [Re(4,4'-(CnH2n+1)(2)-bpy)(CO)(3)Cl] (ReCn; 4,4'-(CnH2n+1)(2)-bpy=4,4'-dialkyl-2,2'-bipyridine) and ruthenium-based photosensitisers [Ru(bpy)(2)(4,4'-(CnH2n+1)(2)-bpy)](PF6)(2) (RuCn) with different alkyl chain lengths (n=0, 9, 12, 15, 17, and 19). We then prepared a series of PEGylated DPPC liposomes containing RuCn and ReCn, hereafter noted C-n, to perform photocatalytic CO2 reduction in the presence of sodium ascorbate. The photocatalytic performance of the C-n liposomes was found to depend on the alkyl tail length, as the turnover number for CO (TON) was inversely correlated to the alkyl chain length, with a more than fivefold higher CO production (TON=14.5) for the C-9 liposomes, compared to C-19 (TON=2.8). Based on immobilisation efficiency quantification, diffusion kinetics, and time-resolved spectroscopy, we identified the main reason for this trend: two types of membrane-bound RuCn species can be found in the membrane, either deeply buried in the bilayer and diffusing slowly, or less buried with much faster diffusion kinetics. Our data suggest that the higher photocatalytic performance of the C-9 system is due to the higher fraction of the more mobile and less buried molecular species, which leads to enhanced electron transfer kinetics between RuC9 and ReC9.Metals in Catalysis, Biomimetics & Inorganic Material

Multimodal super-resolution optical microscopy using a transition metal-based probe provides unprecedented capabilities for imaging both nucle-ar chromatin and mitochondria

Detailed studies on the live cell uptake properties of a dinuclear membrane permeable permeable RuII cell probe show that, at low concentrations, the complex localizes and images mitochondria. At concentrations above ~20 μM the complex images nuclear DNA. Since the complex is extremely photostable, has a large Stokes shift, and displays intrinsic subcellular targeting, its compatibility with super-resolution techniques was investigated. It was found to be very well suited to image mitochondria and nuclear chromatin in two col-our, 2C-SIM; and STED and 3D-STED both in fixed and live cell. In particular, due to its vastly improved photostability compared to conventional SR probes, it can provide images of nuclear DNA at unprecedented resolution

The isolation and secondary functionalisation of the mer- and fac-isomers of tris(5-hydroxymethyl-2,2 '-bipyridine) complexes of ruthenium(II)

Tris-chelate 5-hydroxymethyl-2,2′-bipyridine complexes of ruthenium (II) and the structurally related benzo- and naphthoesters have been isolated. The mer-isomer of the alcohol functionalised complex has been isolated by selective precipitation from methylene chloride and was subsequently functionalised to the benzoester with retention of the geometrical isomerism. The fac- and mer-isomeric forms of the ester complexes were separated using preparative plate silica chromatography and characterised by 1H NMR spectroscopy. X-ray structural analysis of the fac-isomer of both the ester complexes confirmed the product assignment. The photophysical properties of the three isomers were investigated, indicating very similar absorption spectra to [Ru(bipy)3]2+. The emission wavelength was comparable in each case, with the aromatic ester complexes giving a much longer lifetime and higher quantum yield

Electronic and photophysical properties of adducts of [Ru(bpy)₃]²⁺ and Dawson-type sulfite polyoxomolybdates α/β-[Mo₁₈O₅₄(SO₃)₂]⁴⁻

The spectroscopic and photophysical properties of [Ru(bpy)3]2[[Mo18O54(SO3)2], where bpy is 2,2′-bipyridyl and [Mo18O54(SO3)2]4− is either the α or β-sulfite containing polyoxomolybdate isomer, have been measured and compared with those for the well known but structurally distinct sulfate analogue, α-[Mo18O54(SO4)2]4−. Electronic difference spectroscopy revealed the presence of new spectral features around 480 nm, although they are weak in comparison with the [Ru(bpy)3]2[Mo18O54(SO4)2] analogue. Surprisingly, Stern–Volmer plots of [Ru(bpy)3]2+ luminescence quenching by the polyoxometallate revealed the presence of both static and dynamic quenching for both α and β-[Mo18O54(SO3)2]4−. The association constant inferred for the ion cluster [Ru(bpy)3]2α-[Mo18O54(SO4)2] is K = 5.9 ± 0.56 × 106 and that for [Ru(bpy)3]2β-[Mo18O54(SO4)2] is K = 1.0 ± 0.09 × 107. Unlike the sulfate polyoxometalates, both sulfite polyoxometalate–ruthenium adducts are non-luminescent. Despite the strong electrostatic association in the adducts resonance Raman and photoelectrochemical studies suggests that unlike the sulfato polyoxometalate analogue there is no sensitization of the polyoxometalate photochemistry by the ruthenium centre for the sulfite anions. In addition, the adducts exhibit photochemical lability in acetonitrile, attributable to decomposition of the ruthenium complex, which has not been observed for other [Ru(bpy)3]2+ -polyoxometalate adducts. These observations suggest that less electronic communication exists between the [Ru(bpy)3]2+ and the sulfite polyoxoanions relative to their sulfate polyoxoanion counterparts, despite their structural and electronic analogy. The main distinction between sulfate and sulfite polyoxometalates lies in their reversible reduction potentials, which are more positive by approximately 100 mV for the sulfite anions. This suggests that the capacity for [Ru(bpy)3]2+ or analogues to sensitize photoreduction in the adducts of polyoxometalates requires very sensitive redox tuning

Photophysics of ion clusters formed between [Ru(bpy)3] 2+ and the polyoxotungstate anion [S2W18O 62]4-

The interactions between [Ru(bpy)3]2+ and the polyoxotungstate anion [S2W18O62]4- in acetonitrile solution were investigated using a combination of photophysics and optical and Raman spectroscopies. The presence of ion clusters of {[Ru(bpy)3][S2W18O62]}2- (K2 = 7.7 × 105) and [Ru(bpy)3] 2[S2W18O62] (K1 = 1.0 × 106 mol-2 dm-6) are inferred. The 2:1 complex is weakly luminescent, with a lifetime at room temperature of 20 ns under aerobic conditions. Difference electronic absorption, excitation, and resonance Raman spectroscopies indicate that the tungstate anion participates in this transition. Under conditions where [Ru(bpy)3]2+ alone is photolabile, the ion clusters are photostable, with no photodecomposition or photoinduced ligand exchange reactions evident in acetonitrile. This characteristic is examined employing temperature-dependent luminescent studies which demonstrate that the observed activation energy and preexponential factor are considerably different from those of free [Ru(bpy)3]2+ and are characteristic of a photostable polypyridylruthenium complex.SCOPUS: ar.jinfo:eu-repo/semantics/publishe

The influence of molecular mobility on the properties of networks of gold nanoparticles organic ligand

Quantum Matter and Optic

Spin Transition in Arrays of Gold Nanoparticles and Spin Crossover Molecules

Quantum Matter and Optic