G. Christofidis et al. / Polyhedron 31 (2012) 502–505
505
Table 2
structural analysis of the pyridine-2-thione derivative reveals a
slightly distorted tetrahedral geometry around the silver(I) metal
center which is surrounded by the P atoms of the bidentate DPE-
phos and the two S-donor atoms of the py2SH ligands. The S-coor-
dination mode of all the thiones used could be verified by the
appearance of the four characteristic ‘thioamide bands’ in the re-
corded IR spectra of their respective complexes. The new com-
pounds exhibit in the solid state and in solution at room
temperature strong luminescence, with the excited-state responsi-
ble for the emission presumably having a metal perturbed IL char-
acter. Furthermore, there is strong evidence for a participation of
S ? Ag charge transfer in the emissive excited state, the extend
of which could be associated with the electronic characteristics
of the thione ligand.
Selected bond lengths (Å) and angles (o) for 1.
Ag(1)–P(1)
Ag(1)–P(2)
Ag(1)–S(2)
Ag(1)–S(1)
S(1)–C(37)
2.4856(6)
2.5315(6)
2.5437(6)
2.5949(6)
1.706(2)
S(1)–C(37)
N(3)–O(3)
N(3)–O(2)
N(3)–O(4)
1.706(2)
1.217(3)
1.233(3)
1.238(3)
P(1)–Ag(1)–P(2)
P(1)–Ag(1)–S(2)
P(2)–Ag(1)–S(2)
P(1)–Ag(1)–S(1)
P(2)–Ag(1)–S(1)
S(2)–Ag(1)–S(1)
112.20(2)
112.55(2)
106.13(2)
109.59(2)
111.26(2)
104.85(2)
C(37)–S(1)–Ag(1)
C(42)–S(2)–Ag(1)
O(3)–N(3)–O(2)
O(3)–N(3)–O(4)
O(2)–N(3)–O(4)
101.52(8)
108.99(9)
123.7(3)
118.0(3)
118.2(3)
Appendix A. Supplementary data
CCDC 842710 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
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In this paper we describe the synthesis of five novel mixed-li-
gand silver nitrate complexes, bearing the bidentate bis[2-(diphe-
nylphosphano)phenyl]ether and heterocyclic thiones as ligands.
The new complexes are easily formed by the addition of the thione
ligand to the AgNO3–diphosphane adduct in dry acetonitrile. X-ray