Multifunctionality and Nanostructuration in Spin Crossover Materials. A. B. Gaspar ICMOL, University of Valencia

Transcription

1 Multifunctionality and anostructuration in Spin Crossover Materials A. B. Gaspar ICMOL, University of Valencia "WS10-ETOLDs", Valencia 2010

2 Spin Crossover Phenomenon in Fe(II) compounds t 2g e g 10Dq e g 10Dq T, P, hν t 2g E HS -E LS k B T P > 10 Dq High Spin (HS) 5 T 2g Paramagnetic S = 2 P < 10 Dq Low spin (LS) 1 A 1g Diamagnetic S = 0

3 Multifunctionality Magnetic Interactions Liquid Crystals anostructuration anocrystals anoparticles Porosity Guest-absorption SCO LO Films Conductivity

4 Porous SCO polymers Host-guest interactions Guest SCO building blocks Functional guest H 2 O CH 3 OH CO 2 C 2 S O 2 CH 4 H 2 2 I 2 Cl 2 Br 2 SO 2

5 [Fe(pz)Pt(C) 4 ] (pz = pyrazine) Fe Pt channels gate size [(100) and (010) directions]: Å 2 HS state Å 2 LS state T i = 293 K Guest injection V. iel, J. M. Martínez-Agudo, M. C. Muñoz, A. B. Gaspar, J. A. Real, Inorg. Chem., 2001, 40, 3838

6 Bidirectional Chemo-switching of Spin State in the Microporous Framework [Fe(pz)Pt(C) 4 ] Guest molecule Class I Class II Class III Class IV CO 2 H 2 O benzene CS 2 2 D 2 O pyrazine SO 2 O 2 MeOH toluene C 2 H 2 EtOH Thiophene* 2-PrOH acetone Pyrrole* Pyridine* Furan* THF* Molecular size Effect on the spin state Small Small/medium Large Small/medium o High Spin High Spin Low Spin * These clathrates display cooperative spin transitions below 200 K M. Ohba, K. Yoneda, G. Agusti, M. C. Muñoz, A. B. Gaspar, J. A. Real, M. Yamasaki, H. Ando, Y. akao, S. Sakaki, S. Kitagawa, Angew. Chem. Int. Ed., 2009, 48, 4767

7 Synergy Between Gas Absorption and Cooperative SCO Properties: Memory in {Fe(pz)[Pt(C) 4 ]} (1) HS - T T = 293 K Guest injection erasing CS 2 writing Bz erasing LS + T T c T i T i = 293 K T c M. Ohba, K. Yoneda, G. Agusti, M. C. Muñoz, A. B. Gaspar, J. A. Real, M. Yamasaki, H. Ando, Y. akao, S. Sakaki, S. Kitagawa, Angew. Chem. Int. Ed., 2009, 48, 4767

8 M. Ohba, K. Yoneda, G. Agusti, M. C. Muñoz, A. B. Gaspar, J. A. Real, M. Yamasaki, H. Ando, Y. akao, S. Sakaki, S. Kitagawa, Angew. Chem. Int. Ed., 2009, 48, 4767 Synergy Between Gas Absorption and Cooperative SCO Properties: Switch in {Fe(pz)[Pt(C) 4 ]} HS HS sorption desorption T 280 K T 310 K LS -G +G +G -G Start vacuum LS T c T i T c Start MeOH injection at 263 K Time / min.

9 [Fe(pz)Pt(C) 4 ] CS 2 [Fe(pz)Pt(C) 4 ] pz Distances / Å S(1) C(pz) S(2) C(3)S(1) Distances / Å S(2) Pt C(3) C(2)(pz) S(2) C(pz) C(pz) C(pz) C(pz) T = 93 K Pmmm T = 200 K P2/m

10 The structural data of clathrates and the CCSD(T) calculations point to three key factors as the origins of stabilization of the HS and LS states in {Fe(pz)[Pt(C) 4 ]} G: -Size and shape of guest -G pz interaction at site A -G Pt interaction at site B Guest of class II and III Size and shape of guest Guest of class IV -G pz interaction at site A -G Pt interaction at site B

11 Oxidative Addition of Halogens on Open Metal Sites in the Microporous Framework [Fe(pz)Pt(C) 4 ] Cl 2 Br2 I 2 G. Agustí, R. Ohtani, K. Yoneda, A. B. Gaspar, M. Ohba, J. F. Sánchez-Royo, M. C. Muñoz, S. Kitagawa, J. A. Real Angew. Chem. Int. Ed., 2009, 48, 8944

12 Oxidative Addition of Halogens on Open Metal Sites in the Microporous Framework [Fe(pz)Pt(C) 4 ] T = 293 K, P4/mmm {Fe(pz)[Pt(C) 4 (X) p ]} [X = Cl - (p = 1), Br - (p = 1), I - (0 p 1)] Fe(II) C Pt(II) Pt(IV) T /K X - G. Agustí, R. Ohtani, K. Yoneda, A. B. Gaspar, M. Ohba, J. F. Sánchez-Royo, M. C. Muñoz, S. Kitagawa, J. A. Real Angew. Chem. Int. Ed., 2009, 48, 8944

13 Oxidative Addition of Halogens on Open Metal Sites in the Microporous Framework [Fe(pz)Pt(C) 4 ] XPS spectra LS Pt(II) Pt(IV) Pt(II) HS G. Agustí, R. Ohtani, K. Yoneda, A. B. Gaspar, M. Ohba, J. F. Sánchez-Royo, M. C. Muñoz, S. Kitagawa, J. A. Real Angew. Chem. Int. Ed., 2009, 48, 8944

14 anocrystals / anoparticles of SCO polymers

15 anocrystals of [Fe(pz)Pt(C) 4 ] (reverse micelle) I. Boldog, A. B. Gaspar, V. Martínez, P. Pardo-Ibañez, V. Ksenofontov, A. Bhattacharjee, P. Gütlich, J. A. Real, Angew. Chem. Int. Ed., 2008, 47, 6433

16 anocrystals of [Fe(pz)Pt(C) 4 ] (reverse micelle) I. Boldog, A. B. Gaspar, V. Martínez, P. Pardo-Ibañez, V. Ksenofontov, A. Bhattacharjee, P. Gütlich, J. A. Real, Angew. Chem. Int. Ed., 2008, 47, 6433

17 [Fe(3F-py) 2 M(C) 4 ] (M(II) = i, Pd, Pt and 3F-py = 3-fluoropyridine) i/pd/pt Fe C 2/m V. García, A. B. Gaspar, M. C. Muñoz, G. Bukin, G. Levchenko, J. A. Real, Chem. Eur. J., 2009, 15, 10960

18 [Fe(3F-py) 2 i(c) 4 ] [Fe(3F-py) 2 Pd(C) 4 ] 10 5 Pa 0.30 GPa 10 5 Pa 0.12 GPa 0.25 GPa 0.50 GPa [Fe(3F-py) 2 Pt(C) 4 ] 10 5 Pa 0.16 GPa 0.30 GPa V. García, A. B. Gaspar, M. C. Muñoz, G. Bukin, G. Levchenko, J. A. Real, Chem. Eur. J., 2009, 15, 10960

19 [Fe(3F-py) 2 i(c) 4 ] L W anocrystals (reverse micelle) anoparticles (PVP coating polymer) 210x140 nm 400x400x30 nm 70x30 nm

20 [Fe(3F-py) 2 i(c) 4 ] Magnetic properties Mössbauer spectra Light grey: HS Dark grey: LS LS T HS anocrystals 400x400x30 nm anoparticles 70x30 nm V. Martínez, I. Boldog, A. B. Gaspar, V. Ksenofontov, A. Bhattacharjee, P. Gütlich, J. A. Real, 2010, submitted.

21 [Fe(3F-py) 2 Pd(C) 4 ] L anocrystals (reverse micelle) anoparticles (PVP coating polymer) W 480x480x30 nm [Fe(3F-py) 2 Pt(C) 4 ] anocrystals (reverse micelle) 290x180 nm anoparticles (PVP coating polymer) W L 480x480x30 nm 250x180 nm

22 [Fe(3F-py) 2 Pd(C) 4 ] [Fe(3F-py) 2 Pt(C) 4 ] Light grey: HS Dark grey: LS 3b anocrystals 480x480x30 nm anoparticles 290x180 nm anoparticles 250x180 nm V. Martínez, I. Boldog, A. B. Gaspar, V. Ksenofontov, A. Bhattacharjee, P. Gütlich, J. A. Real, 2010, submitted.

23 2D polymer [Fe(3F-py) 2 i(c) 4 ] 3D polymer [Fe(pz)Pt(C) 4 ] * from F. Volatron et al. Inorg. Chem. 2008, 47, 6584 Particle size reduction causes: -Displacement of Tc s to lower temperatures -Decrease of hysteresis width -Appearance of HS and LS residual fractions

24 Fe(II) spin crossover metallomesogens (metal containing liquid crystals)

25 FeII-trenH-Cn-(Cl) 0.5H2O 2+ O 0.5H2 O Fe 2Cl tren = tris(2-aminoethyl)amine O paraffinic layer O ionic bilayer C16 C18 C20 Model compound FeII-trenH-C12-(BF4) Seredyuk, Gaspar, Ksenofontov, Galyametdinov, Kusz, Gütlich, J. Am. Chem. Soc., 2008, 130, 1431 Gaspar, Seredyuk, Gütlich, Coord. Chem. Rev., 2009, 253, 2399

26 Fe II -trenh-c 16 -(Cl) 0.5H 2 O tren = tris(2-aminoethyl)amine O Fe O O 2+ 2Cl 0.5H 2 O Rel. Transm. (%) C 16 χ M T/cm 3 K mol 1 2,0 1,5 1,0 0,5 C 16 T Cr SA = 296 K T = 80 K LS 82 % HS 18 % -2 0 v/mm s Cr S A d/å 0, T/K Seredyuk, Gaspar, Ksenofontov, Galyametdinov, Kusz, Gütlich, J. Am. Chem. Soc., 2008, 130, 1431

27 Fe II -trenh-c n -(Cl) 0.5H 2 O, n = 16, 18, 20 χ M T/cm 3 K mol Cr S A 328 K 311 K C 20 C 18 C 16 Phase transition Cr S A switches on spin-crossover: Coupled systems Polarizing optical microscopy 296 K T/K

28 Polymeric one-dimensional metallomesogens of iron(ii) Fe II -tba-c n -(anion) C n -tba = 3,5-bis(alkoxy)--(4H-1,2,4-triazole-4-yl)benzamide observed when atoms are aligned collinearly Fe Fe Fe Fe Fe 80 K EXAFS data of Fe II -tba-c 12 -(CF 3 SO 3 ) Seredyuk, Gaspar, Ksenofontov, Galyametdinov, Verdaguer, Villain, Gütlich, Inorg.Chem. 2008, 47, 10232

29 (10) alkyl halo Fe Fe, LS XRD of Fe II -tba-c 10 -(tosylate) xh 2 O lg(i) (22) (31) (11) (21) (20) (30) 170 K Alkyl mantle 340 K Fe Fe, HS θ/ Col h Coordination core

30 Fe II -tba-c 10 -(tosylate) (dehydrated) 4 R = O O χ M T/cm 3 K mol DSC: T g = 295 K H Fe R R O Fe m O S O O 2 Seredyuk, Gaspar, Ksenofontov, Reiman, Galyametdinov, Haase, Rentschler, Gütlich, Chem. Mater. 2006, 18, 2513 Rel. Transm. (%) T/K -4 T = 4.2 K LS 53.4(3) % HS 46.6(4) % -2 0 v/mm s

31 χ M T/cm 3 K mol 1 Fe-tba-C n -(tosylate), n = 8, 10, C 8 χ M T/cm 3 K mol K 295 K 265 K g Col h 1 g Col h 1 g Col h T/K T/K Influence of the glass transition; 4 3 C 10 Evolution of the hysteresis width in the homologues; Similar behavior found for Fe-tba-C n -(BF 4 ), n = 8, 10, 12 and Fe-tba-C n -(CF 3 SO 3 ), n = 8, 10, 12 60ºC χ M T/cm 3 K mol C T/K Coupled transitions Chem. Mater. 2006, 18, 2513 Inorg. Chem. 2008, 47, 10232

32 SMOLMAT, ICMOL Valencia Dr. I. Boldog Prof. J. A. Real Prof. M. C. Muñoz Dr. V. Martínez Dr. G. Agustí F. Muñoz

33 Thanks Prof. P. Gütlich, University of Mainz (Germany) Dr. V. Ksenofontov, University of Mainz (Germany) Dr. M. Seredyuk, University of Mainz (Germany) Prof. E. Rentschler, University of Mainz (Germany) Prof. Y. Galyametdinov, Kazan Physical Technical Institute, Russian Academy of Science (Russia) Prof. G. Levchenko, Donetsk Physico-Thechnical Institute, AS of Ukraine Prof. S. Kitagawa, University of Kyoto (Japan) Dr. M. Ohba, University of Kyoto (Japan) MICI, Ministerio de Ciencia e Innovación GVA, Generalitat Valenciana DFG, Deutsche Forschungsgemeinschaft MAGMAET, European etwork of Excellence AvH, Alexander von Humboldt Foundation