Dalton Transactions
Paper
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Conclusions
The crystal structures of 1–3 reveal linear geometry about the
mercury atom via ipso-C and sulphur atoms. Intramolecular
Hg⋯O bonding interactions are observed in 1 and 2. However,
in 3, incorporation of the 3-pyridyl substituent on the ligand
gave rise to (S,S) chelation on the metal together with inter-
molecular Hg⋯N interactions generating a 1-D polymeric
chain motif. These interactions have been assessed by DFT calcu-
lations. 1 and 2 show O,S-coordination while S,S-coordination
is observed in 3. To our knowledge, this is the first time that
S,S-coordination has been observed with β-oxodithioester
ligands and is more likely due to packing effects brought
about by the presence of the N-bonding interactions. These
complexes strongly luminesce in solution and in the solid
phase, which originate from the metal perturbed intra ligand
charge transfer transitions. The somewhat more red shifted
emissions in the solid phase are attributed to the weaker
Hg⋯Hg interactions (1, 2) and the increased conjugation due
to the pyridine lone pair in the extended delocalized structure
in 3. The band gap values suggest the semiconducting nature
of the complexes. This study demonstrates that the mercury(II)
and other heavy main group metal complexes of functiona-
lized β-oxodithioesters may be useful for the design of new
compounds with promising material properties.
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Acknowledgements
Financial support from the Council of Scientific and Industrial
Research (CSIR), New Delhi, project no. 01 (2679)/12/EMR-II
(NS, MKY) and SRF (GR), is gratefully acknowledged and the
Department of Chemistry, CAS-UGC-I, Banaras Hindu Univer-
sity for the X-ray facilities.
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