ISSN:
0947-3440
Keywords:
1,2,4,5-Tetrakis(alkylthio)benzene donors
;
Bromine acceptors
;
Iodine acceptors
;
UV
;
Vis Spectra
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Interactions in Crystals, 111Part 110: Ref.[1]. . - Crystallization and Structure Determination of Donor/Acceptor Complexes between 1,2,4,5-Tetrakis(alkylthio)benzene Derivatives and Bromine or IodineBased on preceding cyclovoltammetric and UV/Vis measurements, red crystals of the donor/acceptor complex {1,2,4,5-tetrakis(ethylthio)benzene…(Br2)2} are grown by using Br2 gasphase diffusion into a CCl4 solution of 1,2,4,5-tetrakis(ethylthio)benzene. In addition, the corresponding iodine complex {1,2,4,5-tetrakis(isopropylthio)benzene⃛(I2)3} is crystallized. The structure determinations prove for the I2 adduct an interesting packing motif, in which two crystallographically independent I2 acceptors bridge each four sulfur donors. The Br2 adduct shows a three-dimensional network with subunits 〉S⃛Br—Br⃛S〈, in which the Br—Br bond is surprisingly elongated by 13 pm (!) relative to the gasphase electron diffraction value for bromine. - The structure discussion is based on iodine acceptor complexes listed in the Cambridge Structural Database and reveals angular-dependent iodine coordination vectors to sulfur as well as a correlation between I—I bond lengths and contact distances S⃛I. Density functional calculations for the model system (H3C)2S⃛Br—Br⃛S(CH3)2 with the experimentally determined structural parameters suggest that a charge of -0.25 is transferred to the BrBr acceptor molecule, which allows to rationalize its 13-pm elongation on complexation to {1,2,4,5-tetrakis(ethylthio)benzene⃛(Br2)2}.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.199619961232
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