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A Study on Electronic Interaction in Dimetallic Complexes with Conjugated Chain

공액사슬로 연결된 이핵금속착체의 전자적 상호작용에 관한 연구

  • Published : 2004.06.01

Abstract

The cis-hex-3-ene-1,5-diynyl-bridged diiron compound 3, [(η$^{5}$ - $C_{5}$ M $e_{5}$ ) Fe(dppe)]$_2$($\mu$-C≡C-CH=CH-C≡C), have been prepared and characterized by cyclic voltammetry(CV), and electronic spectroscopy (UV-VIS and near-IR, NMR). From the results, compound 3 show two well resolved, single-electron, reversible oxidation waves by CV, and comproportionation constant(Kc) calculated from the CV data for compound 3. The Mixed-valence (MV) radical cation 3$^{+}$ show strong absorptions in the near IR, 1586 nm, and this band is more readily assigned as MV $\pi$-$\pi$ band of delocalized complex (Robin-Day Mixed-valence Class III), and the $H_{ab}$ , effective coupling parameter are most consistent with electronic delocalization.

References

  1. R. M. Metzger, 'Unimolecular electrical rectifier', Chem. Rev., 103, p. 3803, 2003 https://doi.org/10.1021/cr020413d
  2. N. Robertson, C. A. McGowan, 'A comparison of potentials molecular wires as components for molecular electronics', Chem. Soc. Rev., 32, p. 96, 2003 https://doi.org/10.1039/b206919a
  3. S. Szafert and J. A. Gladysz, 'Carbon in one dimension: structural analysis of the higher conjugated polyynes', Chem. Rev., 103, p. 4175, 2003 https://doi.org/10.1021/cr030041o
  4. B. S. Brunschwig, C. Creutz, and N. Sutin, 'Optical transitions of symmetrical mixed-valence systems in the Class II-III transition regime', Chem. Soc. Rev., Vol. 31, p. 168, 2002 https://doi.org/10.1039/b008034i
  5. J.-P. Launary, 'Long-distance intervalence electron transfer', Chem. Soc. Rev., Vol. 30, p. 386, 2001 https://doi.org/10.1039/b101377g
  6. J. Tour, 'Molecular wires for electronic applications', Polymer News, Vol. 25, p. 329, 2000
  7. J. Tour, 'Molecular electronics. Synthesis and testing of components', Acc. Chem. Res., Vol. 33, No. 11, p. 791, 2000 https://doi.org/10.1021/ar0000612
  8. E. Emberly and G. Kirczenow, 'Electrical conductance of molecular wires', Nanoechnology, Vol. 10, p. 285, 1999 https://doi.org/10.1088/0957-4484/10/3/311
  9. C. P. Collier, E. W. Wong, M. Belohradsky, F. M. Raymo, J. F. Stoddart, P. J. Kuekes, R. S. Williams, and J. R. Heath, 'Electrically configurable molecular-based logic gates', Science, Vol. 285, p. 391, 1999 https://doi.org/10.1126/science.285.5426.391
  10. A. Kraft, A. C. Grimsdale, and A. B. Holmes, 'Electroluminescent conjugated polymers-Seeing polymers in a new light' Angew. Chem. lnt. Ed., Vol. 37, p. 402, 1998 https://doi.org/10.1002/(SICI)1521-3773(19980302)37:4<402::AID-ANIE402>3.0.CO;2-9
  11. T. Nagamura, 'Novel materials and device for molecular electronics and photonics', CMC, p. 287, 2003
  12. Y. Taniguchi, 'Application of organic semiconductors', CMC, p. 51, 2003
  13. H. Nakazumi, 'Functional dyes in advanced technologies', CMC, p. 46, 2003
  14. J. M. Marshall and D. Dimova-Malinovska, 'Photovoltaic and photoactive materials-properties, technology and application'. Kulwer Academic Pub., p. 97, 2002
  15. M. M. Ward, 'Metal-metal interaction in binuclear complexes exhibiting mixed valency; Molecular wires and switches', Chem. Soc. Rev., Vol. 24, p. 121, 1995 https://doi.org/10.1039/cs9952400121
  16. A. Harriman and R. Ziessel, 'Making photoactive molecular-scale wires', Chem. Commun., p. 1707, 1996
  17. 임은주, 박미화, 윤순일, 이기진, 차덕준, 김진태, '유기발광소자내 정공주입층 Copper(II)-phtalocyanine의 결정 및 광원에 따른 Photocurrent 증폭 연구', 전기전자재료학회논문지, 16권, 7호, p. 622, 2003
  18. 임은주, 한우미, 이정윤, 김명식, 이기진, '"Iron(ll)과 Metal-free phthaocyanine의 결정구조 변화에 따르는 유기발광소자의 발광 특성', 한국전기전자재료학회 2001 하계학술대회논문집, p. 947, 2001
  19. 김정호, 서연호, 박용필, '신 레이저 매질 $Yb(SOL-D)_3$ 착물의 광학적 특성', 한국전기전자재료학회 2001 하계학술대회 논문집, p. 640, 2001
  20. S. Welter, K. Brunner, J. W. Hofstraat, and L. De Cola, 'Electroluminescent device with reversible switching between red and green emission', Nature, Vol. 42, P.52, 2003
  21. L. S. Hung and C. H. Chen, 'Recent progress of molecular organic electroluminescent materials and devices', Mat. Sci.& Eng. reports: A Rev. J., Vol. 39, p. 143, 2002 https://doi.org/10.1016/S0927-796X(02)00093-1
  22. J. Kido and Y. Okamoto, 'Organic lanthanide metal complexes for electroluminescent materials', Chem. Rev., Vol. 102, p. 2357, 2002 https://doi.org/10.1021/cr010448y
  23. F. Paul and C. Lapinte, 'Oragnometallic molecular wires and other nanoscale-sized devices. An approach using the organoiron (dppe)Cp*Fe building block', Coord. Chem. Rev., Vol. 178, p. 431, 1998 https://doi.org/10.1016/S0010-8545(98)00150-7
  24. C. Creutz and H. Taube, 'A direct approach to measuring the franck-codon barrier to electron transfer between metal ions', J. Am. Chem. Soc., Vol. 91, p. 3988, 1969 https://doi.org/10.1021/ja01042a072
  25. M. B. Robin and P. Day, 'Mixed valence chemistry-a survey and classification' Adv. Inorg. Chem. Radiochem., Vol. 10, p. 247, 1967
  26. 정민철, M. Sponsler, '공액사슬을 갖는 철화합물의 전기화학적 특성', 전기전자재료학회논문지, 15권, 호 p. 511, 2002
  27. R. J. McMahon, R. J. halter, R. L. Fimmen, R. J. Wilson, S. A. Peebles, R. L. Kuczkowski, and J. F. Stanton, 'Equilibrium structure of $\mathit{cis}$-hex-3-ene-1,5-diyne and relevance to the Bergman cyclization, J. Am. Chem. Soc., Vol. 122, p. 939, 2000 https://doi.org/10.1021/ja9934908
  28. N. L. Navrvor, L. Toupet, and C. Lapinte, 'Elemental carbon chain bridging two iron centers: syntheses and spectroscopic properties of $[Cp^\ast(dppe)Fe-C_4-FeCp^\ast (dppe)]^{n+}n[PF6]^-$. X-ray crystal structure of the mixed valence complex (n=1)', J. Am. Chem. Soc., Vol. 117, No. 21, p. 7129, 1995 https://doi.org/10.1021/ja00132a013
  29. F. Coat and C. Lapinte, 'Molecular wire consisting of a $C_8$ chain of elemental carbon bridging two metal centers: Synthesis and characterization of $[{Cp^\ast(dppe)Fe}_2-C_8-)]$', Organometallics, Vol. 15, p. 477, 1995 https://doi.org/10.1021/om9507991
  30. F. Coat, F. Paul, C. Lapinte, L. Toupet, K. Costuas, and J.-F. Halet, 'Chemistry of the 1,3,5,7-octatetraynediyl carbon rod end-capped by two electron-rich $(n^5-C_5Me_5)(n^2-dppe)$Fe groups', J. Organomet. Chem. Vol. 683, p. 368, 2003 https://doi.org/10.1016/S0022-328X(03)00709-5
  31. S. L. Stang, F. Paul, and C. Lapinte, 'Molecular wires: Synthesis and properties of the new mixed-valence complex $[Cp^\ast(dppe)Fe-C{\equiv}C-X-C{\equiv}C-FeCp^\ast(dppe)][PF_6] (X=2,5-\;C_4H_2S)$ and comparison of its properties with those of the related all-carbon-bridged complex $(X=\;-C_4-)$', Organometallics, Vol. 19, p. 1035, 2000 https://doi.org/10.1021/om9908231
  32. M.-C. Chung, X. Gu, B.A. Etzenhouser, A. M. Spuches, P. T. Rye, S. K. Seetharaman, D. J Rose, J Zubieta, and M. Sponsler, 'Intermetal coupling in $[(n^5-C_5R_5)Fe(dppe)]_2$ ($\mu$ CH=CHCH=CH) and in their dicationic and monocationic mixed-valence forms', Organometallics, Vol. 22, p. 3485, 2003 https://doi.org/10.1021/om0300979