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Volumn 103, Issue 15, 1999, Pages 2850-2861

Characterization of Chain Molecular Assemblies in Long-Chain, Layered Silver Thiolates: A Joint Infrared Spectroscopy and X-ray Diffraction Study

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EID: 0000664809     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp983938b     Document Type: Article
Times cited : (110)

References (79)
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    • An elegant example of the principle was recently provided by Russell and co-workers [(a) Russell, V. A.; Etter, M. C.; Ward, M. D. J. Am. Chem. Soc. 1994, 116, 1941-1952. (b) Russell, V. A.; Evans, C. A.; Li, W.; Ward, M. D. Science 1997, 276, 575-580.] (not an organic- inorganic hybrid) in the formation of pillared 2D hydrogen-bonded molecular sandwiches wherein the co-assembly of guanidium cations (G) and alkane- substituted sulfonate anions (SR) led to the formation of 2D quasi-hexagonal GS networks via directional hydrogen bonding between (G) NH-O(S) with a concomitant formation of the organic assemblies of R substitents in mono- or bimolecular motif.
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    • An elegant example of the principle was recently provided by Russell and co-workers [(a) Russell, V. A.; Etter, M. C.; Ward, M. D. J. Am. Chem. Soc. 1994, 116, 1941-1952. (b) Russell, V. A.; Evans, C. A.; Li, W.; Ward, M. D. Science 1997, 276, 575-580.] (not an organic-inorganic hybrid) in the formation of pillared 2D hydrogen-bonded molecular sandwiches wherein the co-assembly of guanidium cations (G) and alkane-substituted sulfonate anions (SR) led to the formation of 2D quasi-hexagonal GS networks via directional hydrogen bonding between (G) NH-O(S) with a concomitant formation of the organic assemblies of R substitents in mono-or bimolecular motif.
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    • A previous study (ref 15a) has suggested that the unstable trans (T) form of silver (butane) thiolates is white. The isomerization of the T form to the more stable gauche (G) form is accompanied by the color change from white to yellow. As will be later evident in this manuscript, we find no evidence of any significant population of the G form in colored crystallites of the longer-chain analogues examined here
    • A previous study (ref 15a) has suggested that the unstable trans (T) form of silver (butane) thiolates is white. The isomerization of the T form to the more stable gauche (G) form is accompanied by the color change from white to yellow. As will be later evident in this manuscript, we find no evidence of any significant population of the G form in colored crystallites of the longer-chain analogues examined here.
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    • The presence of non-trans conformation of the methylene group near the S headgroup due to geometric restrictions is not precluded here However, the lack of peaks due to end-gauche conformers, suggests that a gauche structure of these methylenes is not formed in noticeable concentration
    • The presence of non-trans conformation of the methylene group near the S headgroup due to geometric restrictions is not precluded here. However, the lack of peaks due to end-gauche conformers, suggests that a gauche structure of these methylenes is not formed in noticeable concentration.
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    • Note that using assumed Ag-S bond lengths and S-S separation predicts a thickness of ∼0.9 Å for the Ag-S slab
    • Note that using assumed Ag-S bond lengths and S-S separation predicts a thickness of ∼0.9 Å for the Ag-S slab.
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    • In their model of distorted Ag-S lattice for silver butanethiolates, Fijolek and co-workers (ref 15a) note that, the slab thickness increases only marginally to accommodate end-gauche conformers
    • In their model of distorted Ag-S lattice for silver butanethiolates, Fijolek and co-workers (ref 15a) note that, the slab thickness increases only marginally to accommodate end-gauche conformers.
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    • Our recent measurements of low-temperature IR spectra of silver thiolates further confirm that even at very low tempertures, splitting of the rocking and bending modes does not occur
    • Our recent measurements of low-temperature IR spectra of silver thiolates further confirm that even at very low tempertures, splitting of the rocking and bending modes does not occur.


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