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The reaction of ligands based on 3,6-di(2-pyridyl)pyridazine with symmetrical carbocyclic rings fused to the pyridazine ring; 7,10-di(2-pyridyl)-8,9-diazafluoranthene (L1), 1,4-di(2-pyridyl)-6,7,8,9-tetrahydro-5H-cyclo-hepta[d]pyridazine (L2), 1,4-di(2-pyridyl)-5,6,7,8-tetrahydro-phthalazine (L3), 1,4-di(2-pyridyl)-6,7-dihydro-5H-cyclo-penta[d]pyridazine (L4) with silver salts gave a series of complexes (1–7). Characterisation of these using single crystal X-ray structure determination clearly showed that the steric bulk of the carbocycle affects the degree to which pyridine groups remain co-planar with pyridizine, and hence their ability to chelate. The more hindered ligands L1–L3 form a mixture of bischelating and tetrabridging, while the least hindered (L4) was able to chelate exclusively. In the case of L4, the nature of the anion and solvent were also able to affect the outcome of the reaction, with tetrafluoroborate giving the first example of a 4,5-substituted 3,6-di(2-pyridyl)pyridazine ring forming a [2 × 2]-grid.

Structural control: can [2 × 2] silver grids be formed from 4,5-disubstituted 3,6-di(2-pyridyl) pyridazines?