0000000000143639
AUTHOR
Elzbieta Trzop
Guest induced reversible on–off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour
A binary reversible switch between low-temperature multi-step spin crossover (SCO), through the evolution of the population γHS(T) with high-spin (HS)-low-spin (LS) sequence: HS1LS0 (state 1) ↔ HS2/3LS1/3 (state 2) ↔ HS1/2LS1/2 (state 3) ↔ HS1/3LS2/3 (state 4) ↔ HS0LS1 (state 5), and complete one step hysteretic spin transition featuring 20 K wide thermal hysteresis centred at 290 K occurs in the three-dimensional (3D) Hofmann-type porous coordination polymer {FeII(3,8phen)[Au(CN)2]2}·xPhNO2 (3,8phen = 3,8-phenanthroline, PhNO2 = nitrobenzene), made up of two identical interpenetrated pcu-type frameworks. The included PhNO2 guest (x = 1, 1·PhNO2) acts as a molecular wedge between the interp…
Wavelength selective light-induced magnetic effects in the binuclear spin crossover compound{[Fe(bt)(NCS)2]2(bpym)}
Using Fourier transform infrared spectroscopy, x-ray diffraction, and magnetic susceptibility measurements under light irradiation, the selective light-induced excited spin state trapping (LIESST) and the reversible-LIESST effect have been evidenced and studied in depth in the binuclear spin crossover compound {[Fe(bt)(NCS)2]2bpym}. In this system, each magnetic site can switch from low spin (LS) to high spin (HS), so that three states exist, namely, the LS-LS, HS-LS, and HS-HS. All these techniques shine a new light on the high phototunability of this system. In addition to the direct photoswitching from the LS-LS to the HS-LS or to the HS-HS state, here we show that photoinduced switching…
Symmetry breakings in a metal organic framework with a confined guest
The MOF $[{\text{Fe(tvp)}}_{2}{(\text{NCS})}_{2}]\ifmmode\cdot\else\textperiodcentered\fi{}2\text{BzCHO}$ is demonstrated to undergo a complex sequence of phase transitions and spin-crossover behavior of its constitutive ${\text{Fe}}^{\text{II}}$ ions upon adsorption of benzaldehyde guest molecules. Our study, combining Raman and synchrotron x-ray diffraction measurements on a single crystal, reveals that the conversion from the pure high-spin to the pure low-spin phases implies a rich sequence of intermediate phases, with symmetry breaking forming at least three different space groups. These different symmetries involve spin-state ordering, ligand ordering, and guest ordering, interpreted …
Innenrücktitelbild: First Step Towards a Devil's Staircase in Spin-Crossover Materials (Angew. Chem. 30/2016)
Inside Back Cover: First Step Towards a Devil's Staircase in Spin-Crossover Materials (Angew. Chem. Int. Ed. 30/2016)
International audience; Periodic and aperiodic spin-state concentration waves form during “Devil's staircase”-type spin-crossover in a new bimetallic 2D coordination polymer {Fe[(Hg(SCN)3)2](4,4′-bipy)2}n. In their Communication on page 8675 ff., J. A. Real, E. Collet et al. describe the appearance of spin-state concentration waves between long-range spatially ordered structures of low- and high-spin states during multistep spin-crossover.
Formation of local spin-state concentration waves during the relaxation from photoinduced state in a spin-crossover polymer
The complex relaxation from the photoinduced high-spin phase (PIHS) to the low-spin phase of the bimetallic two-dimensional coordination spin-crossover polymer [Fe[(Hg(SCN)3)2](4,4′-bipy)2]nis reported. During the thermal relaxation, commensurate and incommensurate spin-state concentration waves (SSCWs) form. However, contrary to the steps forming at thermal equilibrium, associated with long-range SSCW order, the SSCWs forming during the relaxation from the PIHS phase correspond to short-range order, revealed by diffuse X-ray scattering. This is interpreted as resulting from the competition between the two types of SSCW order and another structural symmetry breaking, due to ligand ordering,…
Impact of the use of sterically congested Ir(III) complexes on the performance of light-emitting electrochemical cells
International audience; The synthesis, structural and optoelectronic characterization of a family of sterically congested cyclometalated cationic Ir(iii) complexes of the form [Ir(C^N)2(dtBubpy)]PF6 (with dtBubpy = 4,4′-di-tert-butyl-2,2′-bipyridine and C^N = a cyclometalating ligand decorated at the 4-position of the pyridine ring and/or the 3-position of the phenyl ring with a range of sterically bulky substituents) are reported. This family of complexes is compared to the unsubstituted analogue complex R1 bearing 2-phenylpyridinato as cyclometalating ligand. The impact of sterically bulky substituents on the C^N ligands on both the solid state photophysics and light-emitting electrochemi…
Competing Phases Involving Spin-State and Ligand Structural Orderings in a Multistable Two-Dimensional Spin Crossover Coordination Polymer
[EN] Competition between spin-crossover and structural ligand ordering is identified as responsible for multistability and generation of six different phases in a rigid two-dimensional coordination polymer formulated {Fe-II[Hg-II(SCN)(3)](2) mu-(4,4'-bipy)(2)}(n) (1) (4,4'-bipy = 4,4'-bipyridine). The structure of 1 consists of infinite linear [Fe(mu-4,4'-bipy)](n)(2n+) chains linked by in situ formed {[Hg-II(SCN)(3)](2)(mu-4,4'-bipy)}(2n-) anionic dimers. The thermal dependence of the high-spin fraction, his, features four magnetic phases defined by steps following the sequence gamma(HS) = 1 (phase 1) gamma(HS) = 1/2 (phase 2) gamma(HS) approximate to 1/3 (phase 3) gamma(HS) = 0 (phase 4) …
CCDC 2016312: Experimental Crystal Structure Determination
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CCDC 1457784: Experimental Crystal Structure Determination
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CCDC 2010363: Experimental Crystal Structure Determination
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CCDC 1457782: Experimental Crystal Structure Determination
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CCDC 1457780: Experimental Crystal Structure Determination
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CCDC 1970081: Experimental Crystal Structure Determination
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CCDC 2010365: Experimental Crystal Structure Determination
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CCDC 1457779: Experimental Crystal Structure Determination
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CCDC 2010361: Experimental Crystal Structure Determination
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Impact of the Use of Sterically Congested Cyclometalated Ligands on the Optoelectronic Properties and Device Performances In Light-Emitting Electrochemical Cells of Cationic Iridium(III) Complexes (dataset)
CCDC 2010360: Experimental Crystal Structure Determination
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CCDC 1970080: Experimental Crystal Structure Determination
Related Article: Céline Mariette, Elzbieta Trzop, Jean-Yves Mevellec, Abdou Boucekkine, Aziz Ghoufi, Guillaume Maurin, Eric Collet, M. Carmen Muñoz, José Antonio Real, Bertrand Toudic|2020|Physical Review B: covering condensed matter and materials physics|101|134103|doi:10.1103/PhysRevB.101.134103
CCDC 2010362: Experimental Crystal Structure Determination
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CCDC 2010366: Experimental Crystal Structure Determination
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CCDC 1970083: Experimental Crystal Structure Determination
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CCDC 1457783: Experimental Crystal Structure Determination
Related Article: Daopeng Zhang, Elzbieta Trzop, Francisco J. Valverde-Muñoz, Lucía Piñeiro-López, M. Carmen Muñoz, Eric Collet, José A. Real|2017|Cryst.Growth Des.|17|2736|doi:10.1021/acs.cgd.7b00218
CCDC 1970082: Experimental Crystal Structure Determination
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CCDC 2010364: Experimental Crystal Structure Determination
Related Article: Lucía Piñeiro-López, Francisco-Javier Valverde-Muñoz, Elzbieta Trzop, M. Carmen Muñoz, Maksym Seredyuk, Javier Castells-Gil, Iván da Silva, Carlos Martí-Gastaldo, Eric Collet, José Antonio Real|2021|Chemical Science|12|1317|doi:10.1039/D0SC04420B
CCDC 1457781: Experimental Crystal Structure Determination
Related Article: Daopeng Zhang, Elzbieta Trzop, Francisco J. Valverde-Muñoz, Lucía Piñeiro-López, M. Carmen Muñoz, Eric Collet, José A. Real|2017|Cryst.Growth Des.|17|2736|doi:10.1021/acs.cgd.7b00218