Infrared Detection with Temperature Sweep for Stability Determination of Ru-ON Metastable States.

A novel method is proposed for studying the thermal decay of the oxygen-coordinated nitrosyl metastable states. Having examined 18 different ruthenium nitrosyl complexes, we observed that, upon photoinduced rotation from Ru-NO to Ru-ON coordination, the frequency of the nitrosyl valence bands shifts, on average, by 126 ± 15 cm-1. The thermal stability of the product Ru-ON state is qualitatively characterized (decay temperature, Arrhenius activation energy, and pre-exponential factor) using infrared absorption of the NO group, in comparison with the reference complex(es), which are all heated in the same KBr disk during temperature sweep.

Two Oxygen-Coordinated Metastable Ru-ON States for Ruthenium Mononitrosyl Complex.

The properties of Ru-ON states were studied in cis-[RuNO(NH3)2(NO2)2OH] under illumination. The structure contains two nonequivalent complexes, and the metastable state was generated for both molecules with 19(1) and 31(1)% populations. The MS1 thermal decay occurs as a one-step process at about 240 K according to differential scanning calorimetry (DSC). For the first-order reaction, the frequency factor and activation energy for the decay process were determined as 2.0(2) × 10(13) s(-1) and 68.3(4) kJ mol(-1), respectively. Also, the simultaneous metastable state decay observed via DSC was in agreement with IR spectroscopy.

Ultrafast Solution-Phase Photophysical and Photochemical Dynamics of Hexaiodobismuthate(III), the Heart of Bismuth Halide Perovskite Solar Cells.

The ultrafast relaxation pathways in a hexaiodide bismuth(III) complex, BiI63-, excited at 530 nm in acetonitrile solution are studied by means of femtosecond transient absorption spectroscopy supported by steady-state absorption/emission measurements and DFT computations. Radiationless relaxation out of the Franck-Condon, largely metal-centered (MC) triply degenerate 3T1u state (46 ± 19 fs), is driven by vibronic coupling due to the Jahn-Teller effect in the excited state. The relaxation populates two lower-energy states: a ligand-to-metal charge transfer (LMCT) excited state of 3π I(5pπ) → Bi(6p) nature and a luminescent "trap" 3A1u(3P0) MC state. Coherent population transfer from the initial 3T1u into the 3π LMCT state occurs in an oscillatory, stepwise manner at ∼190 and ∼550 fs with a population ratio of ∼4:1. The 3π LMCT state decays with a 2.9 ps lifetime, yielding two short-lived reaction intermediates of which the first one reforms the parent ground state with a 15 ps time constant, and the second one decays on a ∼5 ps timescale generating the triplet product species, which persists to the longest 2 ns delay times investigated. This product is identified as the η2 metal-ligated diiodide-bismuth adduct with the intramolecularly formed I-I bond, [(η2-I2)Bi(II)I4]3-, which is the species of interest for solar energy conversion and storage applications. The lifetime of the "trap" 3A1u state is estimated to be 13 ns from the photoluminescence quenching of BiI63-. The findings give insight into the excited-state relaxation dynamics and the photochemical reaction mechanisms in halide complexes of heavy ns2 metal ions.

Metalloligand-based coordination polymer embedding the nitrosyl ruthenium complex for photoactive materials with bound nitric oxide.

The stability of a photoactivated isonitrosyl state was boosted by confining a pre-designed bicarboxylate ligand with a ruthenium nitrosyl fragment in a 2D metal-organic framework. The novel Zn/Ru-based MOF, {Zn[RuNO(H2O)(inic)2(OH)2]2}·12H2O (inic = isonicotinate), was obtained with enhanced isonitrosyl stability by 30 K (up to 200 K) compared to the related ruthenium-only complex.

Stochastic electrochemistry with electrocatalytic nanoparticles at inert ultramicroelectrodes--theory and experiments.

Collisions of several kinds of metal or metal oxide single nanoparticles (NPs) with a less catalytic electrode surface have been observed through amplification of the current by electrocatalysis. Two general types of current response, a current staircase or a current blip (or spike) are seen with particle collisions. The current responses were caused by random individual events as a function of time rather than the usual continuous current caused by an ensemble of a large number of events. The treatment of stochastic electrochemistry like single NP collisions is different from the usual model for ensemble-based electrochemical behaviour. Models for the observed responses are discussed, including simulations, and the frequency of the steps or blips investigated for several systems experimentally.

Femtosecond Excited-State Dynamics and Nitric Oxide Photorelease in a Prototypical Ruthenium Nitrosyl Complex.

Excited-state relaxation of a prototypical ruthenium nitrosyl complex (pentachloronitrosylruthenate) in water is studied by means of ultrafast dispersed, broadband transient absorption spectroscopy. Excitation pulses (duration, 40-70 fs) utilized at seven different wavelengths in the range from 675 to 335 nm populated excited electronic states of different orbital nature. The second excited singlet state of πNO* nature relaxes into the lowest triplet 3πNO* state in 100 fs via the 1d-d intermediate (lowest excited singlet) state with ca. 80 fs lifetime. The 3πNO* lifetime is 3.2 ps, and all three states are inert toward NO release, which happens in less than 200 fs from higher excited states. The vibrational coherences observed are attributed to the Jahn-Teller effect in the 1πNO* state and nitric oxide loss and provide important insights into the nature of the reaction coordinate in the course of the ultrafast excited-state relaxation dynamics.