Bimetallic sandwichlike complexes as novel NLO chromophores

Juergen Heck; Hugo C. Brussard; Sven Dabek; Timo Meyer-Friedrichsen; Hans Wong

doi:10.1117/12.284254

13 October 1997 Bimetallic sandwichlike complexes as novel NLO chromophores

Juergen Heck, Hugo C. Brussard, Sven Dabek, Timo Meyer-Friedrichsen, Hans Wong

Proceedings Volume 3147, Nonlinear Optical Properties of Organic Materials X; (1997) https://doi.org/10.1117/12.284254
Event: Optical Science, Engineering and Instrumentation '97, 1997, San Diego, CA, United States

Abstract

Mono- and dinuclear sesquifulvalene-type complexes [{LnM(l5C5H4)}Z{17C7H6)MLtn}mXm+i (m =0, 1 ; X = BF4, PF6) have been synthesized, particularly with regards to their nonlinear optical properties. Z =-: LM = CpFe, M'L' = -, la; LM = CpFe; M'L' = Cr(CO)3, ib; LM = CpFe, ML',, = RuCp, ic; LM = CpFe, L'M' = RUCP*, id; LM = CpRu; M'L' = -, le; LM =CpRu, M'L' RuCp, if, LM = CpRu, M'L' = RuCp*, ig - Z = C2: LM = CpFe, M'L' = Cr(CO)3, 2 - Z = C2H2:LM = CpFe, ML' = -, 3a; LM = CpFe, M'L' = Cr(CO)3, 3b; LM = CpFe, L'M' = RuCp, 3c; LM = Cp*Fe, M'L' = Cr(CO)3, 3d; LM = (Ph4C4)Co, M'L' = - 5; Z = thiophene-1,5-diyl (C4H2S): LM = CpFe, M'L' = -, 4a; LM = CpFe, M'L' = RuCp) (Cp = C5H5, Cp* C5Me5, Ph = C6H5). The ferrocenyl containing complexes reveal UV/vis spectra, showing long wave absorption bands beyond 550 nm which are assigned to a charge transfer (CT) transition between the cyclo-C5 and cyclo-C-, moieties. The corresponding transitions for the ruthenocenyl compounds if and ig are found below 500 nm. The CT transitions exhibit pronounced negative solvatochromism. Cyclic voltammetry studies and structural data of some of these compounds confirm the strong electronic coupling between the cyclo-C5 and the cyclo-C7 moieties. Hyper Rayleigh scattering (HRS) investigations of these mono- and dinuclear sesquifulvalene derivaties to determine the first hyperpolarizability 13 show several different important features: i) the measured 13 values of compounds with an additional spacer Z are the highest ever obtained for sandwich-type NLO chromophores; ii) the B values of the dinuclear sequifulvalene complexes surpass the 13 values of the mononuclear derivatives markedly; iii) the exchange of a monocationic electron accepting group (Cr(CO)3), with a dicationic one (RuCp) enhances 13 considerably, iv) the use of the (cyclobutadiene)(cyclopentadienyl)Co unit reveals a surprisingly large B value although this compound is mononuclear. The large experimental 13 values are in part assigned to resonance enhancement.

Citation Download Citation

Juergen Heck, Hugo C. Brussard, Sven Dabek, Timo Meyer-Friedrichsen, and Hans Wong "Bimetallic sandwichlike complexes as novel NLO chromophores", Proc. SPIE 3147, Nonlinear Optical Properties of Organic Materials X, (13 October 1997); https://doi.org/10.1117/12.284254

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