A luminescent Pt2Fe spin crossover complex
| Autor: | F. Rupp, Rolf Diller, Mario Ruben, Sergei Lebedkin, Volker Schünemann, Manfred M. Kappes, Fabian Dahms, Juliusz A. Wolny, Hans-Christian Wille, Katharina Chevalier, Isabelle Faus, Thomas Bauer, Olaf Fuhr, Kai Schlage, Bernhard Schäfer |
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| Rok vydání: | 2017 |
| Předmět: |
010405 organic chemistry
Chemistry 010402 general chemistry 01 natural sciences LIESST 0104 chemical sciences Inorganic Chemistry Crystallography Spin crossover Excited state Molecular vibration Ultrafast laser spectroscopy Mössbauer spectroscopy Nuclear resonance vibrational spectroscopy Spectroscopy |
| Zdroj: | Dalton Transactions. 46:2289-2302 |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/c6dt04360g |
| Popis: | 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) 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 Mossbauer 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. |
| Databáze: | OpenAIRE |
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