Janus Scorpionates: Supramolecular Tectons for the Directed Assembly of Hard−Soft Alkali Metallopolymer Chains

A new scorpionate ligand [HB(mtda)3-] containing mercaptothiadiazolyl (mtda) heterocyclic rings with both hard
nitrogen donors and soft sulfur donors has been prepared. This new ligand, the Janus scorpionate, is a hybrid of
a tris(pyrazolyl)borate and a tris(mercaptoimidazolyl)borate. The differential hard/soft character of the dissimilar
donor groups in this bridging ligand was exploited for the controlled solid-state organization of homometallic and
heterometallic alkali metal coordination polymers. Remarkably, in the case of sodium, coordination polymers with
both acentric (with NaS3N3H kernels) and centric (with alternating NaN6 and NaS6H2 kernels) chains are found in
the same crystal (where the centricity is defined by the relative orientations of the B−H bonds of the ligands along
the lattice). For the homometallic potassium congener, the larger cation size, compared to sodium, induced significant
distortions and favored a polar arrangement of ligands in the resulting coordination polymer chain. An examination
of the solid-state structure of the mixed alkali metal salt system revealed that synergistic binding of smaller sodium
cations to the nitrogen portion and of the larger potassium cations to the sulfur portion of the ligand minimizes the
ligand distortions relative to the homometallic coordination polymer counterparts, a design feature of the ligand that
likely assists in thermodynamically driving the self-assembly of the heterometallic chains. The effect of alkali metal
complexation on the solution properties of the ligand was studied by comparing NMR chemical shifts, B−H stretching
frequencies, and electrochemical properties with those of the noncoordinating tetrabutylammonium salt of the
scorpionate. The similarity of these data regardless of cation indicates that the salts are likely dissociated in solution
rather than maintaining their solid-state polymeric structures. This data is augmented by the ESI(±) mass spectral
data for a series of mixed alkali metal tris(mercaptothiadiazolyl)borates that also indicate that dissociation occurs
in solution.