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231223s2009 xx ||||| 00| ||eng c |
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|a pubmed25n1427.xml
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|a (DE-627)NLM19410172X
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|a (NLM)20047010
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|a DE-627
|b ger
|c DE-627
|e rakwb
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|a eng
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|a Kinnibrugh, Tiffany L
|e verfasserin
|4 aut
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|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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|c 2009
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|a Text
|b txt
|2 rdacontent
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|a ohne Hilfsmittel zu benutzen
|b n
|2 rdamedia
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|a Band
|b nc
|2 rdacarrier
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|a Date Revised 29.05.2025
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|a published: Print
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|a Citation Status PubMed-not-MEDLINE
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|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
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|a Journal Article
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|a Salman, Seyhan
|e verfasserin
|4 aut
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|a Getmanenko, Yulia A
|e verfasserin
|4 aut
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|a Coropceanu, Veaceslav
|e verfasserin
|4 aut
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|a Porter, William W
|c 3rd
|e verfasserin
|4 aut
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| 700 |
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|a Timofeeva, Tatiana V
|e verfasserin
|4 aut
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| 700 |
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|a Matzger, Adam J
|e verfasserin
|4 aut
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| 700 |
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|a Brédas, Jean-Luc
|e verfasserin
|4 aut
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| 700 |
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|a Marder, Seth R
|e verfasserin
|4 aut
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| 700 |
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|a Barlow, Stephen
|e verfasserin
|4 aut
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| 773 |
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|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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| 773 |
1 |
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|g volume:28
|g year:2009
|g number:5
|g day:01
|g pages:1350-1357
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|a AR
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|d 28
|j 2009
|e 5
|b 01
|h 1350-1357
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