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A luminescent PtFe spin crossover complex. | LitMetric
A heterotrinuclear [PtFe] spin crossover (SCO) complex was developed and synthesized employing a ditopic bridging bpp-alkynyl ligand L and alkynyl coordinated Pt terpy units: [Fe(L-Pt)](BF) (1). We identified two different types of crystals of 1 which differ in their molecular packing and the number of co-crystallized solvent molecules: 1H (1·3.5CHCl in P1[combining macron]) and 1L (1·10CHCl in C2/c); while 1L shows a reversible SCO with a transition temperature of 268 K, the analogous compound 1H does not show any SCO and remains blocked in the HS state. The temperature-dependent magnetic properties of 1H and 1L were complementarily studied by Mössbauer spectroscopy. It has been shown that 1L performs thermal spin crossover and that 1L can be excited to a LIESST state. The vibrational properties of 1 were investigated by experimental nuclear resonance vibrational spectroscopy. The experimentally determined partial density of vibrational states (pDOS) was compared to a DFT-based simulation of the pDOS. The vibrational modes of the different components were assigned and visualized. In addition, the photophysical properties of 1 and L-Pt were investigated in the solid state and in solution. The ultrafast transient absorption spectroscopy of 1 in solution was carried out to study the PL quenching channel via energy transfer from photoexcited Pt terpy units to the Fe-moiety.
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