Synthesis of a Self-Assembled Hg(II)-Dithiocarbamate Metallomacrocycle

This report illustrates a successful
mercury-directed self-assembly
strategy via the design and synthesis of a new bifunctional bis-dithiocarbamate
ligand K2L. This ligand efficiently self-assembles with
Hg­(II) to afford a novel bimetallic 28-membered macrocycle, Hg2L2. This supramolecular complex persists as a discrete
macrocyclic structure in solution as evidenced by two-dimensional
DOSY NMR. The X-ray diffraction analysis confirms the formation of
the bimetallic metallomacrocycle where both bis-dithiocarbamate units
are asymmetrically bound to the mercury centers. Analysis of noncovalent
interactions in the crystalline state reveals very close Hg···Hg
intramolecular mercurophilic contacts (≈ 3.3 Å) and the
action of C–H···π (chelate) interactions.