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ISCOM’05

ISCOM’05. Hybrid molecular metals based on BEDO-TTF salts with paramagnetic [CrNO(CN) 5 ] 3- and [M(CN) 6 ] 3- anions, M = Fe, Cr. ISCOM’05. Radical cation salts with octahedral metalcomplex anions. ET salts with [M(CN) 6 ] 3- show nonmetallic behavior

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ISCOM’05

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  1. ISCOM’05 Hybrid molecular metals based on BEDO-TTF salts with paramagnetic [CrNO(CN)5]3- and [M(CN)6]3- anions, M = Fe, Cr.

  2. ISCOM’05 Radical cation salts with octahedral metalcomplex anions • ET salts with [M(CN)6]3- show nonmetallic behavior • E. Coronado and P. Day, 2004; L. Ouahab and T. Enoki, 2004 • ET salts with [FeNO(CN)5 ]2- are metals • BO salts [FeNO(CN)5]3-are metals • BO salts are metals, as a rule: • - H. Yamochi, G. Saito, 1993 • BO salts with [M(CN)6]3- are expected to be metals

  3. ISCOM’05 BO salts with [M(CN)6]3- and [CrNO(CN)5]3- anions Synthesis: electrochemical oxidation of BO J- = 0.1 – 0.5 μA, t ~ 10 days BEDO-TTF K3[M(CN)6], M = Fe, Cr, Co DMF, DMF+10%EG, DMF+10%MeOH, DMF+AN, AN+ca1%H2O AN+ca1%H2O, AN+10%EtOH K3[CrNO(CN)6]·H2O 18-crown-6 ether

  4. ISCOM’05 -(BEDO-TTF){A}x -(BO)2[M(CN)6]1/3 -(BO)2.43{K2[CrNO(CN)5]} -(BO)2[CrNO(CN)5]2/3- Type II Type I " - BO2.4{I3} " - BO2{ReO4.H2O} 100x1 200x2 b"mnpxq-T. Mori, Bull. Chem. Soc. Jap, 1998

  5. Type I ISCOM’05 b"- type packing modes of BO molecules b"200x2– BO2{ReO4.H2O} D. Schweitzer et al, 1991 R. Shibaeva, et al, 1992 P2/b b"100x3– BO3{[FeNO(CN)5]0.75[TCE]0.25} P(-1) R. Shibaeva, E. Yagubskii et al, 2000 b"40px3– BO12{[FeNO(CN)5]3[TCE]}

  6. Type I ISCOM’05 BO2[M(CN)6]1/3  Solvy c M = 50%Fe+50%Co: a = 4.027Å b = 10.225Å c = 37.394Å g = 99.17o V= 1520.1Å3 S.G. = Pb R1 = 12% 100x2 a ax3 b 300x2 X-ray diffraction pattern: diffuse 3a-superstructure

  7. Type I ISCOM’05 BO2[M(CN)6]1/2Solvy c a = 8.054Å b = 10.225Å c = 37.394Å g = 99.17o V= 1520.1Å3 AN, H2O 200x2 A+ 2a0 b

  8. Type I ISCOM’05 Type I salts: 1 - BO2{[M(CN)6]0.34·Solvy} -"100x2 BO6{[M(CN)6]1·Solvy} -b"300x2 X-ray: ax3 2 - BO2{[K+0.05M(CN)6]0.40·Solvy} – disordered: "300x2 + "200x2 BO+0.59 • Normal metal-like behavior at low temperatures down to 4.2K • - R(T): R300K/R4.2K~ 15, σ300K ~ 50 om-1cm-1

  9. Type I ISCOM’05 3 - BO2[CrNO(CN)5]0.58 Solvy} disordered* *Incommensurate sublattice of the close packed octahedral anions in the channels of the BO sublatice BO3.44{[Cr(CN)6]1Solvy} (BO)2{[CrNO(CN)5]2/3-Solvy},  ~ 0.08 Raman Spectroscopy: BO+0.5 (BO)2{A+x[CrNO(CN)5]2/3-Solvy}, x = 0.74

  10. Type I ISCOM’05 2 - BO2{(Ax[CrNO(CN)5])0.58}

  11. ISCOM’05 -(BEDO-TTF){A}x 1 - -(BO)2[M(CN)6]1/3Solvy -(BO)2.43{K2[CrNO(CN)5]} 2 - -(BO)2Kx[CrNO(CN)5]2/3-Solvy,  ~ 0.08 Type II Type I " - BO2.4{I3} " - BO2{ReO4.H2O} 100x1 200x2

  12. Type II ISCOM’05 b"- type packing modes of BO molecules c Cl, H20 Anion layer units c BF4, H2O b b BO2.4(I3) -F. Wudl, H. Yamochi et al, 1990. BO3Cu2(NCS)3 – J.M. Williams et al,1990. BO2Cl(H2O)x – R.P.Shibaeva, E.B. Yagubskii et al, 1999 BO2BF4(H2O)x – S. Khasanov, H. Yamochi, G. Saito, 2001 (private commun.) 100x1

  13. Type II ISCOM’05 -(BO)2.43{K2[CrNO(CN)5]} BO sublattice: a2 = 3.994 Åα2 = 95.29 º b2 = 5.355 Åβ2 = 94.40 º c2 = 19.303 Åγ2 = 98.74 º V2 = 404.5 Å3 R1 = 4.8% Anion sublattice: a1 = 4.520 Å α1 = 91.43 º b1 = 4.336 Å β1 = 93.96 º c1 = 19.212 Åγ1 = 119.14 º V1 = 327.5 Å3 R1 = 9.2% √3x√3-Superstructure is diffuse

  14. Type II ISCOM’05 -(BO)2.43{K2[CrNO(CN)5]}

  15. Type II - (BO)2.43{K2[CrNO(CN)5]} Incommensurate BO and anion sublattices ISCOM’05 a2 b2 a1 b1 Area per anion unit,{K2 [CrNO(CN)5]} d = = 3S1:S2= 3b1: b2= 2.43 Area per BO  - (BO){K2[CrNO(CN)5]}0.412

  16. Type II ISCOM’05 -(BO){K2-x[CrNO(CN)5]}y 1. Synthesis with H2O BO{[K2CrNO(CN)5]0.409} incommensurate BO2.44{[K2CrNO(CN)5]} BO12 {[K2CrNO(CN)5]5-} :  = 0 - superstructure Raman Spectroscopy: BO+0.41 2. Synthesis with EtOH BO+0.44 BO{[K2-xCrNO(CN)5]0.35·Solvy}, x = 0.25 (X-ray diffraction: 3xb1 structure in anion layer, b2:3b1 = 0.4 -> substitution for both potassium and anion by solvent)

  17. Type II ISCOM’05 BO2.72 {[K1.92CrNO(CN)5] ·Solvy} Synthesis with EtOH: BO{[K1.92CrNO(CN)5]0.37·Solvy}

  18. Type II ISCOM’05 BO2.72 {[K1.92CrNO(CN)5] ·Solvy}

  19. Summary • Conducting salts of BO with paramagnetic [M(CN)6]3- and • [CrNO(CN)5]3- have been synthesized; • - Crystal structures of two salts have been solved: • - -(BO)2{[M(CN)6]1/3Solvy}, • - -(BO)2.43{[K2CrNO(CN)5]}; • It is shown that the incommensurate or disordered structures • of “-type open the possibility to control charge transfer • degree • All the salts show metallic behavior at low temperatures; • Incommensurate sublattices of paramagnetic anions • show low-dimensional behavior of spin system.

  20. ISCOM’05 Synthesis: Dubrovskii, T. Prokhorova, N. Spitsina, A. Kazakova, N. Kushch, L. Buravov, E. Yagubskii,1Institute of Problem of Chemical Physics, Chernogolovka Crystal structure analysis: S. Simonov, L. Zorina, S. Khasanov, R. Shibaeva, 2Institute of Solid State Physics,Chernogolovka Magnetic and optical measurements: R. Morgunov3,1, Y. Tanimoto3,4,O. Drozdova3, 3Institute of Molecular Science, Okazaki 4Hirosima University, Higashi-Hirosima

  21. Type II ISCOM’05 -(BO){K2[CrNO(CN)5]}d: Incommensurate BO and anion sublattices a2 b2 a1 b1 K+→Rb+,Cs+, (Et4N)+… Area per BO d = = S2:3S1= b2:3b1 = 0.412 Area per charge in anion layer, {K2 [CrNO(CN)5]}1- Charge transfer is dependent on the complementary units in anion layer

  22. ISCOM’05 References • E. Coronado and P. Day, Chem. Rev., 104, 5419 (2004). • L. Ouhab and T. Enoki, Eur. J. Inorg. Chem., 5, 933 (2004). • S. Kalich, D. Schweitzer, I. Heinen, S.E. Lan, B. Nuber, H.J. Keller, K. Winzer, and H. W. Helberg, Solid State Commun., 8, 191, (1991). • L. I. Buravov, A.G. Khomenko, N.D. Kushch, V. N. Laukhin, A. I. Schegolev, E. B. Yagubskii, L. P. Rozenberg, and R. P. Shibaeva, J. Phys. I, France, 2, 529 (1992). • F. Wudl, H. Yamochi, T. Suzuki, H. Isolato, C. Fite, H. Kasmai, K. Liou, G. Srdanov, P. Coppens, K. Maly, and A. Frost-Jensen, J. Amer. Chem. Soc., 112, 2461 (1990).

  23. ISCOM’05 b’’- type packing modes of BO molecules a b (Van-der-Waals spheres) a = 4.1A, b = 5.3A, g = 98o A C B H. Yamochi,G. Saito et al, 1996

  24. ISCOM’05 b’’- type packing modes of BO molecules RA-overlapping mode in the stacks BO: the ability of self-aggregation into regular stacks is very high

  25. ISCOM’05 b’’- type packing modes of BO molecules B-B-B… A B b’’10 A-A-B-A-A-B… A-B-A-B… b’’10x3 b’’10x2 BO self-aggregation ability is not complete: Probability of occurrence of stacking faults in the side-by-side sequence is high !

  26. ISCOM’05 b502

  27. Type I ISCOM’05 b"- type packing modes of BO molecules Effect of large anion in b"m0x2 structures 34.0Å 37.7Å d d + 1.85Å C-C ~ 6Å b"20x2– BO2{ReO4.H2O} b"10x2 – BO2{[M(CN)6]1/3·Solvx}

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