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Issue 7, 2017
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A luminescent Pt2Fe spin crossover complex

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A heterotrinuclear [Pt2Fe] spin crossover (SCO) complex was developed and synthesized employing a ditopic bridging bpp-alkynyl ligand L and alkynyl coordinated PtII terpy units: [FeII(L-PtII)2]2(BF4)2 (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 (1·3.5CH2Cl2 in P[1 with combining macron]) and 1L (1·10CH2Cl2 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 PtII terpy units to the FeII-moiety.

Graphical abstract: A luminescent Pt2Fe spin crossover complex

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The article was received on 16 Nov 2016, accepted on 12 Jan 2017 and first published on 30 Jan 2017

Article type: Paper
DOI: 10.1039/C6DT04360G
Citation: Dalton Trans., 2017,46, 2289-2302
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    A luminescent Pt2Fe spin crossover complex

    B. Schäfer, T. Bauer, I. Faus, J. A. Wolny, F. Dahms, O. Fuhr, S. Lebedkin, H. Wille, K. Schlage, K. Chevalier, F. Rupp, R. Diller, V. Schünemann, M. M. Kappes and M. Ruben, Dalton Trans., 2017, 46, 2289
    DOI: 10.1039/C6DT04360G

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