ausblenden:
Schlagwörter:
Dynamics, experimental and computational details
Zusammenfassung:
The dynamics of the photodriven charge transfer-
induced spin transition (CTIST) in two Fe/Co Prussian Blue
Analogues (PBAs) are revealed by femtosecond IR and UV/vis
pump−probe spectroscopy. Depending on temperature, the known
tetranuclear square-type complex [Co 2 Fe 2 (CN) 6 (tp*) 2 (4,4′-
dtbbpy) 4](PF 6)2 (1) exists in two electronic states. In acetonitrile
solution, at <240 K, the low temperature (LT) phase is prevalent
consisting of low-spin Fe(II) and low-spin Co(III), [Fe IILS CoIIILS]2 .
Temperature rise is the reason behind thermally-induced CTIST
toward the high temperature (HT) phase consisting of low-spin
Fe(III) and high-spin Co(II), [FeIIILSCoIIHS ]2, being prevalent at
>300 K. Photoexcitation into the intervalence charge transfer
(IVCT) band of the LT phase at 800 nm induces electron transfer in one Fe−Co edge of PBA 1 and produces a [Fe IIILSCoIILS ]
intermediate which by spin-crossover (SCO) is stabilized within 400 fs to a long-lived (>1 ns) [Fe IIILSCo IIHS] species. In contrast,
IVCT excitation of the HT phase at 400 nm generates a [Fe IILSCoIIIHS] species with a lifetime of 3.6 ps. Subsequent back-electron
transfer populates the vibrationally hot ground state, which thermalizes within 8 ps. The newly synthesized dinuclear PBA,
[CoFe(CN)3(tp*)(pz*4Lut)]ClO 4 (2), provides a benchmark of the HT phase of 1, i.e., [Fe IIILSCo IIHS], as verified by variable
temperature magnetic susceptibility measurements and 57 Fe Mö ssbauer spectroscopy. The photoinduced charge transfer dynamics
of PBA 2 indeed are almost identical to that of the HT phase of PBA 1 with a lifetime of the excited [Fe IILSCoIIIHS ] species of 3.8 ps.
