Shamrock 303i spectrograph

All compounds for TRLFS experiments were used as received. Methanol (absolute) was purchased from Merck and stored over molecular sieves. The concentration of Cm(iii) was set to 6.6 × 10^–8 mol × L^–1 by adding an aliquot of a stock solution [Cm(iii)] = 6.7 × 10^–6 mol L^–1 in HClO₄ (1.0 × 10^–2 mol L^–1) to the [²⁴³Am({¹⁵N}C5-BPP)₃](OTf)₃ NMR sample. The isotopic mass distribution of the Cm(iii) solution was 89.7% ²⁴⁸Cm, 9.4% ²⁴⁶Cm, <0.5% ²⁴³Cm, ²⁴⁴Cm, ²⁴⁵Cm, and ²⁴⁷Cm, determined by alpha spectroscopy and ICP-MS. TRLFS measurements were performed using a Nd:YAG-pumped dye laser system [Surelite II laser (Continuum), NARROWscan D-R dye laser (Radiant Dyes Laser Accessories)]. For Cm(iii) excitation a wavelength of 396.6 nm was used. The emission spectra were recorded at an angle of 90° to the exciting laser beam. A Shamrock 303i spectrograph (ANDOR), equipped with a 300, 900 and 1200 lines per mm grating turret was used for spectral decomposition. Fluorescence spectra were recorded in the 575–635 nm range using the 1200 lines per mm grating of the spectrograph. The fluorescence emission was detected by an ICCD camera [iStar Gen III, A-DH 720 18F-63 (ANDOR)]. Rayleigh scattering and shortlived fluorescence of organic ligands was discriminated by a delay time of 1.0 μs before the fluorescence light is recorded. The quartz cuvette was temperature controlled at T = 25 °C.