Abstract
Infinite molecular helices [Ag(3,3′-Py2S)]X (3,3′-Py2S = 3,3′-thiobispyridine; X- = BF4 -, ClO4 -, and PF6 -) have been rationally constructed or induced. Crystallographic characterization (X- = BF4 -, monoclinic P21/n, a = 8.946(3) Å, b = 14.130(2) Å, c = 10.124(2) Å, β = 107.83(2)°, V = 1218.3(5) Å3, Z = 4, R = 0.0351; X- = ClO4 -, monoclinic P21/n, a = 8.884(1) Å, b = 14.305(3) Å, c = 10.110(1) Å, β = 106.78(1)°, V = 1230.1(3) Å3, Z = 4, R = 0.0417; X- = PF6 -, monoclinic P21/c, a = 10.959(2) Å, b = 9.808(2) Å, c = 14.065(3) Å, β = 112.03(2)°, V = 1401.4(5) Å3, Z = 4, R = 0.0442) reveals that the skeletal structure is an oblong cylindrical cationic helix consisting of alternating Ag(I) and 3,3′-Py2S species and that its counteranions are pinched in two columns inside each helix. The formation of the helical coordination polymer appears to be primarily associated with a suitable combination of the skewed conformer of 3,3′-Py2S and the potential linear geometry of the N-Ag(I)-N bond. However, the framework of the nitrate analogue [Ag(3,3′-Py2S)NO3] (monoclinic P21/c, a = 8.177(2) Å, b = 10.291(1) Å, c = 14.771(2) Å, β = 102.19(1)°, V = 1214.9(4) Å3, Z = 4, R = 0.0300) is a two-dimensional network consisting of an 18-membered ring unit, where each 3,3′-Py2S acts as a N,N′,S- tridentate ligand connecting three tetrahedral silver(I) ions with the monodentate nitrate weakly bonded to the silver (Ag···O = 2.65(1) Å) rather than acting as a counteranion. The anion exchange of [Ag(3,3′-Py2S)-NO3] with BF4 -, ClO4 -, or PF6 - has been accomplished in aqueous media. The two-dimensional networks are easily converted into the helices via the anion exchange, but the reverse anion exchange proceeds slightly. Thermal analyses indicate a relationship between the thermal stabilities and the structural properties.
| Original language | English |
|---|---|
| Pages (from-to) | 2105-2110 |
| Number of pages | 6 |
| Journal | Inorganic Chemistry |
| Volume | 40 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - 2001 Apr 23 |
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- Inorganic Chemistry
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Structures and related properties of AgX bearing 3,3′-thiobispyridine (X- = NO3 -, BF4 -, ClO4 -, and PF6 -). / Jung, O. S.; Kim, Y. J.; Lee, Y. A.; Chae, H. K.; Jang, Ho Gyeom; Hong, J.
In: Inorganic Chemistry, Vol. 40, No. 9, 23.04.2001, p. 2105-2110.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Structures and related properties of AgX bearing 3,3′-thiobispyridine (X- = NO3 -, BF4 -, ClO4 -, and PF6 -)
AU - Jung, O. S.
AU - Kim, Y. J.
AU - Lee, Y. A.
AU - Chae, H. K.
AU - Jang, Ho Gyeom
AU - Hong, J.
PY - 2001/4/23
Y1 - 2001/4/23
N2 - Infinite molecular helices [Ag(3,3′-Py2S)]X (3,3′-Py2S = 3,3′-thiobispyridine; X- = BF4 -, ClO4 -, and PF6 -) have been rationally constructed or induced. Crystallographic characterization (X- = BF4 -, monoclinic P21/n, a = 8.946(3) Å, b = 14.130(2) Å, c = 10.124(2) Å, β = 107.83(2)°, V = 1218.3(5) Å3, Z = 4, R = 0.0351; X- = ClO4 -, monoclinic P21/n, a = 8.884(1) Å, b = 14.305(3) Å, c = 10.110(1) Å, β = 106.78(1)°, V = 1230.1(3) Å3, Z = 4, R = 0.0417; X- = PF6 -, monoclinic P21/c, a = 10.959(2) Å, b = 9.808(2) Å, c = 14.065(3) Å, β = 112.03(2)°, V = 1401.4(5) Å3, Z = 4, R = 0.0442) reveals that the skeletal structure is an oblong cylindrical cationic helix consisting of alternating Ag(I) and 3,3′-Py2S species and that its counteranions are pinched in two columns inside each helix. The formation of the helical coordination polymer appears to be primarily associated with a suitable combination of the skewed conformer of 3,3′-Py2S and the potential linear geometry of the N-Ag(I)-N bond. However, the framework of the nitrate analogue [Ag(3,3′-Py2S)NO3] (monoclinic P21/c, a = 8.177(2) Å, b = 10.291(1) Å, c = 14.771(2) Å, β = 102.19(1)°, V = 1214.9(4) Å3, Z = 4, R = 0.0300) is a two-dimensional network consisting of an 18-membered ring unit, where each 3,3′-Py2S acts as a N,N′,S- tridentate ligand connecting three tetrahedral silver(I) ions with the monodentate nitrate weakly bonded to the silver (Ag···O = 2.65(1) Å) rather than acting as a counteranion. The anion exchange of [Ag(3,3′-Py2S)-NO3] with BF4 -, ClO4 -, or PF6 - has been accomplished in aqueous media. The two-dimensional networks are easily converted into the helices via the anion exchange, but the reverse anion exchange proceeds slightly. Thermal analyses indicate a relationship between the thermal stabilities and the structural properties.
AB - Infinite molecular helices [Ag(3,3′-Py2S)]X (3,3′-Py2S = 3,3′-thiobispyridine; X- = BF4 -, ClO4 -, and PF6 -) have been rationally constructed or induced. Crystallographic characterization (X- = BF4 -, monoclinic P21/n, a = 8.946(3) Å, b = 14.130(2) Å, c = 10.124(2) Å, β = 107.83(2)°, V = 1218.3(5) Å3, Z = 4, R = 0.0351; X- = ClO4 -, monoclinic P21/n, a = 8.884(1) Å, b = 14.305(3) Å, c = 10.110(1) Å, β = 106.78(1)°, V = 1230.1(3) Å3, Z = 4, R = 0.0417; X- = PF6 -, monoclinic P21/c, a = 10.959(2) Å, b = 9.808(2) Å, c = 14.065(3) Å, β = 112.03(2)°, V = 1401.4(5) Å3, Z = 4, R = 0.0442) reveals that the skeletal structure is an oblong cylindrical cationic helix consisting of alternating Ag(I) and 3,3′-Py2S species and that its counteranions are pinched in two columns inside each helix. The formation of the helical coordination polymer appears to be primarily associated with a suitable combination of the skewed conformer of 3,3′-Py2S and the potential linear geometry of the N-Ag(I)-N bond. However, the framework of the nitrate analogue [Ag(3,3′-Py2S)NO3] (monoclinic P21/c, a = 8.177(2) Å, b = 10.291(1) Å, c = 14.771(2) Å, β = 102.19(1)°, V = 1214.9(4) Å3, Z = 4, R = 0.0300) is a two-dimensional network consisting of an 18-membered ring unit, where each 3,3′-Py2S acts as a N,N′,S- tridentate ligand connecting three tetrahedral silver(I) ions with the monodentate nitrate weakly bonded to the silver (Ag···O = 2.65(1) Å) rather than acting as a counteranion. The anion exchange of [Ag(3,3′-Py2S)-NO3] with BF4 -, ClO4 -, or PF6 - has been accomplished in aqueous media. The two-dimensional networks are easily converted into the helices via the anion exchange, but the reverse anion exchange proceeds slightly. Thermal analyses indicate a relationship between the thermal stabilities and the structural properties.
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UR - http://www.scopus.com/inward/citedby.url?scp=0035937904&partnerID=8YFLogxK
U2 - 10.1021/ic001072u
DO - 10.1021/ic001072u
M3 - Article
C2 - 11304156
AN - SCOPUS:0035937904
VL - 40
SP - 2105
EP - 2110
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 9
ER -