title: A luminescent Pt2Fe spin crossover complex.
abstract: A heterotrinuclear [Pt2Fe] spin crossover (SCO) complex was developed and synthesized employing a ditopic bridging bpp-alkynyl ligand L and alkynyl coordinated PtIIterpy 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 (1·3.5CH2Cl2in P1[combining macron]) and 1L (1·10CH2Cl2in 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 PtIIterpy units to the FeII-moiety.
authors.affiliation: Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Campus Nord, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany. Mario.Ruben@kit.edu.
authors.forename: Bernhard
authors.identifier: http://orcid.org/0000-0002-8007-6261
authors.initials: B
authors.lastname: Schäfer
authors.affiliation: Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Bauer
authors.affiliation: Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern, Germany.
authors.forename: Isabelle
authors.initials: I
authors.lastname: Faus
authors.affiliation: Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern, Germany.
authors.forename: Juliusz A
authors.initials: JA
authors.lastname: Wolny
authors.affiliation: Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern, Germany.
authors.forename: Fabian
authors.initials: F
authors.lastname: Dahms
authors.affiliation: Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Campus Nord, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany. Mario.Ruben@kit.edu and Karlsruhe Nano-Micro Facility (KNMF), Karlsruher Institut für Technologie (KIT), Campus Nord, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Olaf
authors.initials: O
authors.lastname: Fuhr
authors.affiliation: Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Campus Nord, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany. Mario.Ruben@kit.edu.
authors.forename: Sergei
authors.initials: S
authors.lastname: Lebedkin
authors.affiliation: Deutsches Elektronen-Synchrotron, Notkestr. 85, D-22607 Hamburg, Germany.
authors.forename: Hans-Christian
authors.initials: HC
authors.lastname: Wille
authors.affiliation: Deutsches Elektronen-Synchrotron, Notkestr. 85, D-22607 Hamburg, Germany.
authors.forename: Kai
authors.initials: K
authors.lastname: Schlage
authors.affiliation: Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern, Germany.
authors.forename: Katharina
authors.initials: K
authors.lastname: Chevalier
authors.affiliation: Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern, Germany.
authors.forename: Fabian
authors.initials: F
authors.lastname: Rupp
authors.affiliation: Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern, Germany.
authors.forename: Rolf
authors.initials: R
authors.lastname: Diller
authors.affiliation: Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern, Germany.
authors.forename: Volker
authors.initials: V
authors.lastname: Schünemann
authors.affiliation: Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Campus Nord, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany. Mario.Ruben@kit.edu and Institut für Physikalische Chemie, Karlsruher Institut für Technologie (KIT), Fritz-Haber-Weg 2, 76131 Karlsruhe, Germany.
authors.forename: Manfred M
authors.initials: MM
authors.lastname: Kappes
authors.affiliation: Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Campus Nord, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany. Mario.Ruben@kit.edu and Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), CNRS-Université de Strasbourg, 23, rue du Loess, BP 43, 67034 Strasbourg cedex 2, France.
authors.forename: Mario
authors.initials: M
authors.lastname: Ruben