Coupled Potential Energy Surfaces Strongly Impact the Lowest-Energy Spin-Flip Transition in Six-Coordinate Nickel(II) Complexes.

Luminescent complexes of earth-abundant first-row transition metals are of renewed, broad interest due to their spectroscopic and photochemical properties as well as emerging applications. New strong-field polypyridine ligands have led to six-coordinate 3d3 chromium(III) complexes with intense spin-flip luminescence in solution at room temperature. The ground and emissive states both arise from the (t2)3 electron configuration involving the dπ levels (O point group symmetry labels). Pseudoctahedral 3d8 nickel(II) complexes with such strong ligands are a priori also promising candidates for spin-flip luminescence. In contrast, the relevant electron configurations involve the dσ orbitals and (e)2 configurations. We have prepared the known nickel(II) complexes [Ni(terpy)2]2+, [Ni(phen)3]2+, and [Ni(ddpd)2]2+ as well as the novel complexes [Ni(dgpy)2]2+ and [Ni(tpe)2]2+ forming a series with increasing ligand field strengths (terpy = 2,2':6',2″-terpyridine; phen = 1,10-phenanthroline; ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine; dgpy = 2,6-diguanidylpyridine; tpe = 1,1,1-tris(pyrid-2-yl)ethane). The lowest-energy singlet and triplet excited states of these nickel(II) complexes are analyzed based on absorption spectra using ligand field theory and CASSCF-NEVPT2 calculations for vertical transition energies and a model based on coupled potential energy surfaces, leading to calculated absorption spectra in good agreement with the experimental data. No photoluminescence signal was observed in the wavelength ranges identified through the analyses of the absorption spectra. The models provide insight into key differences between the nickel(II) complexes and their strongly luminescent chromium(III) analogues.

SARS-CoV-2 Receptor Binding Domain as a Stable-Potential Target for SARS-CoV-2 Detection by Surface-Enhanced Raman Spectroscopy.

In this work, we report a new approach for detecting SARS-CoV-2 RBD protein (RBD) using the surface-enhanced Raman spectroscopy (SERS) technique. The optical enhancement was obtained thanks to the preparation of nanostructured Ag/Au substrates. Fabricated Au/Ag nanostructures were used in the SERS experiment for RBD protein detection. SERS substrates show higher capabilities and sensitivity to detect RBD protein in a short time (3 s) and with very low power. We were able to push the detection limit of proteins to a single protein detection level of 1 pM. The latter is equivalent to 1 fM as a detection limit of viruses. Additionally, we have shown that the SERS technique was useful to figure out the presence of RBD protein on antibody functionalized substrates. In this case, the SERS detection was based on protein-antibody recognition, which led to shifts in the Raman peaks and allowed signal discrimination between RBD and other targets such as Bovine serum albumin (BSA) protein. A perfect agreement between a 3D simulated model based on finite element method and experiment was reported confirming the SERS frequency shift potential for trace proteins detection. Our results could open the way to develop a new prototype based on SERS sensitivity and selectivity for rapid detection at a very low concentration of virus and even at a single protein level.

Highly emissive polymorphs of anhydrous cadmium tetracyanoplatinate and their solvated coordination networks.

Two anhydrous polymorphs of cadmium cyanoplatinate Cd[Pt(CN)4] coordination polymers have been synthesized and thermally, spectroscopically, and structurally characterized. α-Cd[Pt(CN)4] and ß-Cd[Pt(CN)4] are densely packed, highly emissive 3-D solids, with quantum yields of 0.85 (λem = 520 nm) and 0.79 (λem = 448 nm) respectively. Their mutual hydrate, Cd(H2O)[Pt(CN)4]·2H2O, forms a complex 3-D coordination polymer with Cd-O-Cd bridges and Pt-Pt interactions. Additionally, exposure of solid α-Cd[Pt(CN)4] and ß-Cd[Pt(CN)4] to several solvent vapours results in the formation of 2-D cyanometallate sheets of the adduct compounds CdL2[Pt(CN)4] (L = DMSO, DMF, and pyridine). Cd(pyridine)2[Pt(CN)4] shows a significantly lower quantum yield (0.32) in comparison to the parent Cd[Pt(CN)4] coordination polymers. Upon heating CdL2[Pt(CN)4] preferentially forms the kinetic product α-Cd[Pt(CN)4].

Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry.

In spite of intense, recent research efforts, luminescent transition metal complexes with Earth-abundant metals are still very rare owing to the small ligand field splitting of 3d transition metal complexes and the resulting non-emissive low-energy metal-centered states. Low-energy excited states decay efficiently non-radiatively, so that near-infrared emissive transition metal complexes with 3d transition metals are even more challenging. We report that the heteroleptic pseudo-octahedral d2-vanadium(iii) complex VCl3(ddpd) (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) shows near-infrared singlet → triplet spin-flip phosphorescence maxima at 1102, 1219 and 1256 nm with a lifetime of 0.5 µs at room temperature. Band splitting, ligand deuteration, excitation energy and temperature effects on the excited state dynamics will be discussed on slow and fast timescales using Raman, static and time-resolved photoluminescence, step-scan FTIR and fs-UV pump-vis probe spectroscopy as well as photolysis experiments in combination with static quantum chemical calculations. These results inform future design strategies for molecular materials of Earth-abundant metal ions exhibiting spin-flip luminescence and photoinduced metal-ligand bond homolysis.

Optical near-field mapping of plasmonic nanostructures prepared by nanosphere lithography.

We introduce a simple, fast, efficient and non-destructive method to study the optical near-field properties of plasmonic nanotriangles prepared by nanosphere lithography. Using a rectangular Fourier filter on the blurred signal together with filtering of the lower spatial frequencies to remove the far-field contribution, the pure near-field contributions of the optical images were extracted. We performed measurements using two excitation wavelengths (532.1 nm and 632.8 nm) and two different polarizations. After the processing of the optical images, the distribution of hot spots can be correlated with the topography of the structures, as indicated by the presence of brighter spots at the apexes of the nanostructures. This technique is validated by comparison of the results to numerical simulations, where agreement is obtained, thereby confirming the near-field nature of the images. Our approach does not require any advanced equipment and we suggest that it could be applied to any type of sample, while keeping the measurement times reasonably short.