Probing the Impact of Solvation on Photoexcited Spin Crossover Complexes with High-Precision X‑ray Transient Absorption Spectroscopy

Investigating the photoinduced electronic and structural response of bistable molecular building blocks incorporating transition metals in solution phase constitutes a necessary stepping stone for steering their properties toward applications and performance optimizations. This work presents a detailed X-ray transient absorption (XTA) spectroscopy study of a prototypical spin crossover (SCO) complex [Fe^II(mbpy)₃]²⁺ (where mbpy = 4,4′-dimethyl-2,2′-bipyridine) with an [Fe^IIN₆] first coordination shell in water (H₂O) and acetonitrile (CH₃CN). The unprecedented data quality of the XTA spectra together with the direct fitting of the difference spectra in <i>k</i> space using a large number of scattering paths enables resolving the subtle difference in the photoexcited structures of an Fe^II complex in two solvents for the first time. Compared to the low spin (LS) ¹A₁ state, the average Fe–N bond elongations for the photoinduced high spin (HS) ⁵T₂ state are found to be 0.181 ± 0.003 Å in H₂O and 0.199 ± 0.003 Å in CH₃CN. This difference in structural response is attributed to ligand–solvent interactions that are stronger in H₂O than in CH₃CN for the HS excited state. Our studies demonstrate that, although the metal center of [Fe^II(mbpy)₃]²⁺ could have been expected to be rather shielded by the three bidentate ligands with quasi-octahedral coordination, the ligand field strength in the HS excited state is nevertheless indirectly affected by solvation effects that modifies the charge distribution within the Fe–N covalent bonds. More generally, this work highlights the importance of including solvation dynamics in order to develop a generalized understanding of the spin-state switching at the atomic level

CO₂ Preactivation in Photoinduced Reduction via Surface Functionalization of TiO₂ Nanoparticles

Salicylate and salicylic acid derivatives act as electron donors via charge-transfer complexes when adsorbed on semiconducting surfaces. When photoexcited, charge is injected into the conduction band directly from their highest occupied molecular orbital (HOMO) without needing mediation by the lowest unoccupied molecular orbital (LUMO). In this study, we successfully induce the chemical participation of carbon dioxide in a charge transfer state using 3-aminosalicylic acid (3ASA). We determine the geometry of CO₂ using a combination of ultraviolet–visible spectroscopy (UV–vis), surface enhanced Raman scattering (SERS), ¹³C NMR, and electron paramagnetic resonance (EPR). We find CO₂ binds on Ti sites in a carbonate form and discern via EPR a surface Ti-centered radical in the vicinity of CO₂, suggesting successful charge transfer from the sensitizer to the neighboring site of CO₂. This study opens the possibility of analyzing the structural and electronic properties of the anchoring sites for CO₂ on semiconducting surfaces and proposes a set of tools and experiments to do so

Layer-by-Layer Assembled Films of Perylene Diimide- and Squaraine-Containing Metal–Organic Framework-like Materials: Solar Energy Capture and Directional Energy Transfer

We demonstrate that thin films of metal–organic framework (MOF)-like materials, containing two perylenediimides (<b>PDICl</b>_<b>4</b>, <b>PDIOPh</b>_<b>2</b>) and a squaraine dye (<b>S1</b>), can be fabricated by layer-by-layer assembly (LbL). Interestingly, these LbL films absorb across the visible light region (400–750 nm) and facilitate directional energy transfer. Due to the high spectral overlap and oriented transition dipole moments of the donor (<b>PDICl</b>_<b>4</b> and <b>PDIOPh</b>_<b>2</b>) and acceptor (<b>S1</b>) components, directional long-range energy transfer from the bluest to reddest absorber was successfully demonstrated in the multicomponent MOF-like films. These findings have significant implications for the development of solar energy conversion devices based on MOFs

Probing the Anisotropic Distortion of Photoexcited Spin Crossover Complexes with Picosecond X‑ray Absorption Spectroscopy

For numerous spin crossover complexes, the anisotropic distortion of the first coordination shell around the transition metal center governs the dynamics of the high-spin/low-spin interconversion. However, this structural parameter remains elusive for samples that cannot be investigated with crystallography. The present work demonstrates how picosecond X-ray absorption spectroscopy is able to capture this specific deformation in the photoinduced high-spin state of solvated [Fe­(terpy)₂]²⁺, a complex which belongs to the prominent family of spin crossover building blocks with nonequivalent metal–ligand bonds. The correlated changes in Fe–N_Axial, Fe–N_Distal, and bite angle N_Distal–Fe–N_Axial extracted from the measurements are in very good agreement with those predicted by DFT calculations in <i>D</i>_2<i>d</i> symmetry. The outlined methodology is generally applicable to the characterization of ultrafast nuclear rearrangements around metal centers in photoactive molecular complexes and nanomaterials, including those that do not display long-range order