Conformational flexibility of the hinge-like H2L (2,2'-bislawsone or 3-hydroxy-1,4-napthoquinone) due to its free rotation about the central C-C single bond involving two hydroxynaphthoquinone units provides structural diversities particularly on metalation (Mn, Zn, Ni) including supramolecular assemblies, zig-zag, helix, square, and coordination polymers. The primary thrust was therefore to scrutinize structural aspects and their application potential in aqueous organic flow and therefore lithium-ion batteries. The present deliberation is however intended to highlight the hitherto unexplored binding features of deprotonated H2L with the selective heavier metal ions such as Ru and Os. In this context, the reaction of H2L with the metal precursors such as {Ru(bpy)2}/{Ru(acac)2} led to the formation of L2- bridged dimeric complexes [(bpy)2RuII(µ-L2-)RuII(bpy)2](ClO4)2 [1](ClO4)2 (S=0)/(acac)2RuIII(µ-L2-)RuIII(acac)2 2 (S=1) and seven-membered chelate derived monoruthenium framework (pap)2Ru(L2-) 3 (S=0) in presence of {Ru(pap)2} metal fragment. The same reaction of H2L with the corresponding osmium metal precursors {Os(bpy)2} and {Os(pap)2} remarkably afforded monomeric [(bpy)2OsII(L12-)] 4 (S=0) and [(pap)2OsII(L12-)] 5 (S=0), (Figure) respectively, where one of the hydroxynaphthoquinone units of H2L was transformed to 1,3-dioxoindan via the insitu C-C bond activation step. The detailed experimental and theoretical studies revealed (i) molecular identities of the complexes, (ii) mechanistic event of the transformation process and (iii) bidirectional non-innocence of L2- under the stated selective coordination situations.

Structural functionalities of hinge-like deprotonated bis-lawsone on ruthenium and osmium platforms

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