Synthesis and Nonlinear Optical Properties of 5-Monocyclopentadienyliron(II) Acetylide Derivatives. X-ray Crystal Structure

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• 作者：M. Helena Garcia ; M. Paula Robalo ; Alberto R. Dias ; M. Teresa Duarte ; Wim Wenseleers ; G. Aerts ; Etienne Goovaerts ; Marie P. Cifuentes ; Steph Hurst ; Mark G. Humphrey ; Marek Samoc ; and Barry Luther-Davi
• 刊名：Organometallics
• 出版年：2002
• 出版时间：May 13, 2002
• 年：2002
• 卷：21
• 期：10
• 页码：2107 - 2118
• 全文大小：191K
• 年卷期：v.21,no.10(May 13, 2002)
• ISSN：1520-6041

文摘

A series of new acetylide complexes of the type [Fe(mages/gifchars/eta.gif" BORDER=0 >⁵-C₅H₅)(Pmages/entities/arcraise.gif">P)(p-Cmages/entities/tbd1.gif">CC₆H₄R)] (Pmages/entities/arcraise.gif">P =DPPE (=1,2-bis(diphenylphosphino)ethane), (R)-PROPHOS (=(R)-(+)-1,2-bis(diphenylphosphino)propane), R = NO₂, C₆H₄NO₂, (Z)-C(H)=C(H)C₆H₄NO₂, (E)-C(H)=C(H)C₆H₄NO₂) havebeen synthesized by halide abstraction from the precursors [Fe(mages/gifchars/eta.gif" BORDER=0 >⁵-C₅H₅)(Pmages/entities/arcraise.gif">P)(I)] and fullycharacterized. Quadratic hyperpolarizabilities (mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">) for the complexes have been determinedby hyper-Rayleigh scattering at 1064 nm. The influence on the nonlinear response of acetylidechain length in proceeding from 4-nitrophenylethynyl to 4-nitrobiphenylethynyl and 4-nitro-(E)-stibenylethynyl has been studied, revealing values of the first hyperpolarizabilities amongthe highest reported for organometallic molecular materials. Comparisons on the nonlinearefficiencies are drawn with the related well-known families of compounds [Ru(mages/gifchars/eta.gif" BORDER=0 >⁵-C₅H₅)(PR₃)₂(p-Cmages/entities/tbd1.gif">C-(aryl)-NO₂)] and [Fe(mages/gifchars/eta.gif" BORDER=0 >⁵-C₅H₅)(Pmages/entities/arcraise.gif">P)(p-Nmages/entities/tbd1.gif">C-(aryl)-NO₂)]⁺. Cubic hyperpolarizabilities (mages/gifchars/gamma.gif" BORDER=0 >) determined by Z-scan at 800 nm are consistent with an increase in mages/gifchars/gamma.gif" BORDER=0 >upon replacing Ru by the more easily oxidizable Fe and upon chain-lengthening thedelocalizable mages/gifchars/pi.gif" BORDER=0 >-bridging unit (proceeding from 4-C₆H₄ to (E)-4,4'-C₆H₄CH=CHC₆H₄). X-raycrystallographic structures of complexes [Fe(mages/gifchars/eta.gif" BORDER=0 >⁵-C₅H₅)(DPPE)(p-Cmages/entities/tbd1.gif">CC₆H₄NO₂)] and [Fe(mages/gifchars/eta.gif" BORDER=0 >⁵-C₅H₅)(DPPE)((E)-p-Cmages/entities/tbd1.gif">CC₆H₄C(H)=C(H)C₆H₄NO₂)] were studied in order to investigate theexistence of mages/gifchars/pi.gif" BORDER=0 >-back-donation suggested by spectroscopic and electrochemical data. Crystalpacking was analyzed with the aim of assessing the alignment of the molecules in the latticeand hence suggesting the magnitude of NLO properties at the macroscopic level.