We report that an equilibrium mixture of triangular and square supramolecular species results when the flexible, ditopic donor unit, trans-bis(4-pyridyl)ethylene, is reacted with the ditopic acceptor unit, cis-(Me(3)P)(2)Pt(OTf)(2), in a one-to-one ratio. Both products are characterized in solution, by way of multinuclear NMR, and in the solid state, via X-ray crystallography. The effects of water and anions, cobalticarborane versus triflate, on the equilibrium are probed. The selective crystallization of either of the two species can be accomplished via the appropriate choice of solvents and ratio of anions present in the system. The dominant species in solution is not always consistent with the most prevalent species in the solid state.

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Tetraferrocenyl[5]cumulene (Fc) 2 CdCdCdCdCdC(Fc) 2 (Fc ) ferrocenyl) is synthesized from 1,1-diferrocenyl-1-methoxypropyne by formal dimerization of diferrocenylethenylidenecarbene generated in situ by deprotonation and elimination of methoxide. The cumulene is an air-stable compound of blue color with an electron-rich cumulene moiety, as indicated by various spectroscopic methods. In contrast to other (shorter) ferrocenyl cumulenes which show no reactivity due to steric hindrance, (Fc) 2 CdCdCdCdCdC(Fc) 2 is a quite reactive compound, as exemplified by (i) transition metal complex formation with Rh(I), (ii) [3]ferrocenophane generation by Ni(0)-promoted intramolecular electrophilic aromatic substitution, and (iii) [2+2] cycloaddition with olefins and alkynes, and (iv) [2+2] cycloaddition with C 60 and C 70 , yielding the first cumulene derivatives of fullerenes. MS, UV-vis, IR, Raman, NMR, cyclic voltammetry, controlled potential coulometry, Mössbauer spectroscopy, and X-ray single-crystal structure analysis have been performed to characterize the new compounds.

[formula: see text] Utilizing coordination as a motif, the self-organization of six ditopic and four tritopic building blocks leads to the formation of nanoscale adamantanoid frameworks.