Electrochemical Properties of Diiron Complexes wish Conjugated Chains

공액 사슬을 갖는 철 화합물의 전기화학적 특성

  • ;
  • Micheal b. Sponsler
  • Published : 2002.06.01


The complex 1 $([Cp*Fe(CO)_2]_2-(\mu-CH=CH-CH=CH))$ which have butadiene as a bridge were synthesized from $Cp*(CO)_2FeK$ and cis-3,4-dichlorocyclobutene. The derivatives of complex 1 where one or two carbonyl groups are replaced by phosphine ligands have been prepared by photochemical substitution. The new derivatives $([Cp*Fe(L)_2]_2-(\mu-CH=CH-CH=CH))$ where L = $(Ph_2PCH_2CH_2PPh_2)$ and $([Cp*Fe(CO)(L)]_2-(\mu-CH=CH-CH=CH))$ where L : $PPh_3$ have been characterized from $^^1H-$, $^^13C-$,$^^31P-NMR$ and elemental analysis. Obtained complexes have been studied in electrochemical experiment and UV/VIS-near-IR. The mixed-valence radical cation forms of complex 2, 3 species were found to be delocalized as the Class III. Based on the separation of the waves ($\triangle E$ : 0.470 ~ 0.605 V), the efficiency of electronic communication between two metal centers of cation species leading to stabilization relative to neutral species. The phosphine-substitute complexes (2, 3) displays two reversible oxidation waves and oxidation state of metal centers-dependent color change, electrochromism, was observed from yellow to orange and deep blue in methylene chloride.


  1. J. Am. Chem. Soc. v.122 A conjugal consanguineous family of butadiyneidiyl-derived complexes : synthesis and electronic ground states of neutral, radical cationic and dicationic Iron/Rhenium C₄species F.Paul;W.E.Meyer;L.Toupet;H.Jiao;J.A.Gladysz;C.Lapinte
  2. J. Chem. Soc., Dalton Trans. An Efficent Synthesis of Polyynyl and Polyynediyl Complexes of Ruthenium(Ⅱ) M.I.Bruce;B.C.Hall;B.D.Kelly;P.J.Low;B.W.Skelton;A.H.White
  3. J. Am. Chem. Soc. v.121 Electronic communication between metal centers across unsaturated alkylidyne ligands A.Mayr;M.P.Y.Yu;V.W.W.Yam
  4. J. Am. Chem. Soc. v.122 Oxidation chemistry of metal-bonded C.Chains : A Combined chemical, spectroelectro-chemical and computational study M.I.Bruce;P.J.Low;K.Costuas;J.F.Halet;S.P.Best;G.A.Heath
  5. 전기전자재료학회논문지 v.15 no.2 Photoacry을 게이트 절연층으로 사용한 유기 박막트랜지스터의 전기적 특성에 관한 연구 김윤명;표상우;김준호;심재훈;김영관;김정수
  6. 한국전기전자재료학회 2001하계학술대회논문집 Iron(Ⅱ)과 Metal-free phthaocyanine의 결정 구조변화에 따르는 유기발광소자의 발광 특성 임은주;한우미;이정윤;김명식;이기진
  7. 한국전기전자재료학회 2001하계학술대회논문집 신 레이저매질 Yb(SOL-D)₃착물의 광학적 특성 김정호;서연호;박용필
  8. J. Am. Chem. Soc. v.92 The organic solid state electron transfer in a mixed valence salt of biferrocene D.O.Cowan;F.Kaufman
  9. Adv. Inorg. Chem. Radiochem. v.10 Mixed valence chemistry - a survey and classification M.B.Robin;P.Day
  10. J. Am. Chem. Soc. v.91 A direct approach to measuring the franck-condon barrier to electron transfer between metal ions C.Creutz;H.Taube
  11. J. Am. Chem. Soc. v.122 Toward metal capped one-dimensional carbon allotropes : wirelike C6-C20 polyynediyl chains that span two redox-active(η5-C5Me5)Re(NO)(PPh₃) endgroups R.Dembinski;T.Bartik;B.Bartik;M.Jaeger;J.A.Gladysz
  12. Inorg. Chem. v.27 Photophysical, photochemical and redox behavior of a series of ligand-bridge (OC)5M-L-M'(CO)5 (M, M' - Cr, Mo, W)complexes M.M.Zulu;A.J.Lees
  13. J. Am. Chem. Soc. v.117 Elemental carbon chain bridging two iron centers : syntheses and spectroscopic properties of [Cp(dppe)Fe-C₄-FeCp(dppe)]n+ n[PF6], X-ray crystal structure of the mixed valence complex (n=1) N.L.Narvor;L.Toupet;C.Lapinte