962. Search for spectral evidence of expansion of the valency shell of sulphur in aromatic sulphides

Mangini, Anna; Passerini, R.

doi:10.1039/jr9560004954

Cited by 17 publications

(4 citation statements)

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“…The aniline derivatives 12a , b , and 14a , b all exhibited two-band absorption features with comparable oscillation strength, although 14 showed clear fine structures (Figure c). Varying the amino substituents from phenyl to methyl in 12a , b led to 5- and 9-nm blue-shifts for each band, respectively, which were consistent with the UV spectra in cyclohexane of triphenylamine (λ max = 301 nm) and dimethylaniline (λ max = 295 nm) …”

Section: Resultssupporting

confidence: 71%

“…Varying the amino substituents from phenyl to methyl in 12a,b led to 5-and 9-nm blue-shifts for each band, respectively, which were consistent with the UV spectra in cyclohexane of triphenylamine (λ max ) 301 nm) 29 and dimethylaniline (λ max ) 295 nm). 30 However, the phenyl-to-methyl substitution in 14 resulted in very small shifts in the opposite direction (ca. 3 nm for both bands), indicating a difference in donor-acceptor interactions through the butadiyne bridge.…”

Section: Resultsmentioning

confidence: 98%

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Molecular Wires Comprising π-Extended Ethynyl- and Butadiynyl-2,5-Diphenyl-1,3,4-Oxadiazole Derivatives: Synthesis, Redox, Structural, and Optoelectronic Properties

et al. 2006

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2,5-Diphenyl-1,3,4-oxadiazole (OXD) derivatives with terminal ethynyl- (4a,b) and butadiynyl- (8a,b) substituents have been synthesized in high yields. 2-Methyl-3,5-hexadiyn-2-ol has not been exploited previously in the synthesis of terminal butadiynes. Crystals of 8a and 8b are remarkably stable to long-term storage under ambient conditions. The X-ray crystal structure of 8a reveals that the butadiyne moieties are spatially isolated by the aromatic moieties, which explains the high stability. Two series of derived pi-conjugated molecules, Donor-(C[triple bond]C)(n)-OXD (n = 1, 2) and OXD-(C[triple bond]C)(n)-Donor-(C[triple bond]C)(n)-OXD (n = 1) [Donor = tetrathiafulvalene (TTF), bithiophene, 9-(4,5-dimethyl-1,3-dithiol-2-ylidene)fluorene, and triphenylamine], have been synthesized using Sonogashira reactions and characterized by X-ray crystallography, cyclic voltammetry, and optical absorption/emission spectroscopy. The electron-withdrawing effect of the OXD units is manifested by a positive shift of the donor oxidation waves in these systems: the butadiynylene spacer (n = 2) further shifts the first oxidation waves by 40-80 mV compared to analogues n = 1. The absorption spectra of TTF-OXD hybrids 10d and 11 are blue-shifted by 80 nm compared to the bithienyl-bridged derivative 10f and are similar to the butadiynyl-OXD building-block 8a, demonstrating that conjugation is disrupted by a neutral TTF unit. Solutions of the TTF-OXD and 9-(4,5-dimethyl-1,3-dithiol-2-ylidene)fluorene-OXD hybrids, 10d, 10g, 11, and 13, are only very weakly fluorescent due to quenching from the electron-donor moieties. In contrast, the triphenylamine-OXD hybrids 12a, 12b, 14a, and 14b are fluorescent; the PLQYs of the butadiynylene derivatives 14a and 14b are lower than those of the ethynylene-bridged analogues 12a and 12b.

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Section: Resultssupporting

confidence: 71%

Section: Resultsmentioning

confidence: 98%

Molecular Wires Comprising π-Extended Ethynyl- and Butadiynyl-2,5-Diphenyl-1,3,4-Oxadiazole Derivatives: Synthesis, Redox, Structural, and Optoelectronic Properties

et al. 2006

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“…Because of the pyramidal (sp3) geometry at the sulfur compared to the planar (sp2) geometry at the carbon, the bonding and stereochemistry of the sulfinyl esters should differ from those of the analogous carboxylic esters. 15 In our previous studies,16 we reported the high stability of fluorinated carboxylic esters with substituents other than fluorine on the alkoxy -carbon atom toward fluoride ion attack. Comparison of the relative stabilities of the trifluoromethylsulfinates, RfOS(0)CF3, with those of the fluorinated carboxylic esters was of interest since the sulfur(IV) in these esters was expected to be a more reactive site than carbon in the carboxylic esters.…”

Section: Introductionmentioning

confidence: 95%

Trifluoromethylsulfinyl esters of fluorinated alcohols

Majid¹,

Shreeve²

1974

Inorg. Chem.

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Reactions of trifluoromethylsulfinyl fluoride, CF3SOF, with fluoro alcohols in the presence of NaF(CsF) were used to prepare a series of new sulfinate esters of the general formula RfOS(0)CF3 (R¡ = CF3(CH3)CH, CF3(CH3),C, (CF3)2CH, (CF3)2C(CH3), CF3(CF2C1)CH). Perfluoro-ierf-butyl trifluoromethylsulfinate, (CF3)3C0S(0)CF3, was prepared by the reaction of trifluoromethylsulfinyl chloride, CF3SOCl, with the (CF3)3COH-Me3N adduct. The reaction of GIF with (CF3)2 CH0S(0)CF3 resulted in the cleavage of the S-CF3 bond to give (CF3)2C(H)0S(0)F. Because of a chiral sulfurcenter, the methyl groups in CF3(CH3)2C0S(0)CF3 and the trifluoromethyl groups in (CF3)2 C(H)OS(0)CF3 and (CF3)2-C(H)0S(0)F are magnetically nonequivalent. The nmr spectra of CF3(CH3)CH0S(0)CF3 and CF3(CF2C1)CH0S(0)CF3 showed the presence of two diastereoisomers. With the exception of CF3(CH3)CH0S(0)CF3, all of the trifluoromethylsulfinates are decomposed by CsF in the 25-100°t emperature range. Infrared, mass, and nmr spectra and elemental analysis data are reported.Table III. Infrared Spectra of RfOS(0)CF3 (cm'1)

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“…Although the spectral behavior of p-nitro-p '-aminodiphenyl sulfide has been interpreted by Szmant and McIntosh (182) as indicative of electron-transmitting ability by the sulfur atom bridge, more extensive work (128,131,132,133) disposes of this conclusion, and also for 3-amino-6-nitrodibenzothiophene (XXVIII) (130). o2n^^NH.…”

Section: XXVmentioning

confidence: 99%