Dipolar Second-Order Nonlinear Optical Chromophores Containing Ferrocene, Octamethylferrocene, and Ruthenocene Donors and Strong π-Acceptors : Crystal Structures and Comparison of π-Donor Strengths

Crystal structures have been determined for six dipolar polyene chromophores with metallocenyl - ferrocenyl (Fc), octamethylferrocenyl (Fc″), or ruthenocenyl (Rc) - donors and strong heterocyclic acceptors based on 1,3-diethyl-2-thiobarbituric acid or 3-dicyanomethylidene-2,3-dihydrobenzothiophene-1...

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Veröffentlicht in:Organometallics. - 1998. - 28(2009), 5 vom: 01., Seite 1350-1357
1. Verfasser: Kinnibrugh, Tiffany L (VerfasserIn)
Weitere Verfasser: Salman, Seyhan, Getmanenko, Yulia A, Coropceanu, Veaceslav, Porter, William W 3rd, Timofeeva, Tatiana V, Matzger, Adam J, Brédas, Jean-Luc, Marder, Seth R, Barlow, Stephen
Format: Aufsatz
Sprache:English
Veröffentlicht: 2009
Zugriff auf das übergeordnete Werk:Organometallics
Schlagworte:Journal Article
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100 1 |a Kinnibrugh, Tiffany L  |e verfasserin  |4 aut 
245 1 0 |a Dipolar Second-Order Nonlinear Optical Chromophores Containing Ferrocene, Octamethylferrocene, and Ruthenocene Donors and Strong π-Acceptors  |b Crystal Structures and Comparison of π-Donor Strengths 
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520 |a Crystal structures have been determined for six dipolar polyene chromophores with metallocenyl - ferrocenyl (Fc), octamethylferrocenyl (Fc″), or ruthenocenyl (Rc) - donors and strong heterocyclic acceptors based on 1,3-diethyl-2-thiobarbituric acid or 3-dicyanomethylidene-2,3-dihydrobenzothiophene-1,1-dioxide. In each case, crystals were found to belong to centrosymmetric space groups. For one example, polymer-induced heteronucleation revealed the existence of two additional polymorphs, which were inactive in second-harmonic generation, suggesting that they were also centrosymmetric. The bond-length alternations between the formally double and single bonds of the polyene bridges are reduced compared to simple polyenes, indicating significant contribution from charge-separated resonance structures, although the metallocenes are not significantly distorted towards the [(η(6)-fulvene)(η(5)-cyclopentadienyl)metal(II)](+) extreme. DFT geometries are in excellent agreement with those determined crystallographically; while the π-donor strengths of the three metallocenyl groups are insufficiently different to result in detectable differences in the crystallographic bond-length alternations, the DFT geometries, as well as DFT-calculations of partial charges for atoms, suggest that π-donor strength decreases in the order Fc″ ≫ Fc > Rc. NMR, IR and electrochemical evidence also suggests that octamethylferrocenyl is the stronger π-donor, exhibiting similar π-donor strength to a p-(dialkylamino)phenyl group, while ferrocenyl and ruthenocenyl show very similar π-donor strengths to one another in chromophores of this type 
650 4 |a Journal Article 
700 1 |a Salman, Seyhan  |e verfasserin  |4 aut 
700 1 |a Getmanenko, Yulia A  |e verfasserin  |4 aut 
700 1 |a Coropceanu, Veaceslav  |e verfasserin  |4 aut 
700 1 |a Porter, William W  |c 3rd  |e verfasserin  |4 aut 
700 1 |a Timofeeva, Tatiana V  |e verfasserin  |4 aut 
700 1 |a Matzger, Adam J  |e verfasserin  |4 aut 
700 1 |a Brédas, Jean-Luc  |e verfasserin  |4 aut 
700 1 |a Marder, Seth R  |e verfasserin  |4 aut 
700 1 |a Barlow, Stephen  |e verfasserin  |4 aut 
773 0 8 |i Enthalten in  |t Organometallics  |d 1998  |g 28(2009), 5 vom: 01., Seite 1350-1357  |w (DE-627)NLM098167103  |x 0276-7333  |7 nnas 
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