BODIPY-based Ru(II) and Ir(III) organometallic complexes of avobenzone, a sunscreen material: Potent anticancer agents.

The use of organic compounds with known medicinal properties in the synthesis of metal-based complexes is an important alternative to improve the biological activity of metal-based drugs. The reaction of [M(arene)Cl] (M = Ru, arene = p-cymene and M = Ir, arene = pentamethylcyclopentadienyl, cp*) with avobenzone (1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione, AVBH) and KOH in methanol leads to the formation of the neutral complexes [Ru(p-cymene)(AVB)Cl] 1 and [Ir(cp*)(AVB)Cl] 2 (cp* = pentamethylcyclopentadienyl). Subsequent reaction of 1 and 2 with pyridyl derivative-BODIPY ligands, BDP and BDPCC (BODIPY = boron dipyrromethene, BDP = 4-dipyridine boron dipyrromethene, BDPCC = 4-ethynylpyridine boron dipyrromethene) in methanol gives a series of four new dicationic supramolecules: [Ru(p-cymene)(AVB)BDP][2CFSO] 3, [Ir(cp*)(AVB)BDP][2CFSO] 4, [Ru(p-cymene)(AVB)BDPCC][2CFSO] 5 and [Ir(cp*)(AVB)BDPCC][2CFSO] 6.

The Orientation of Silver Surfaces Drives the Reactivity and the Selectivity in Homo-Coupling Reactions.

Original reaction pathways can be explored in the on-surface synthesis approach where small aromatic precursors are confined to the surface of single crystal metals. The bis-indanedione molecule reacted with itself on silver surfaces in different ways, through a Knoevenagel reaction or an oxidative coupling, leading to the formation of a variety of new molecular compounds and covalently-linked 1D or 2D networks. Noteworthy, original reaction products were obtained that cannot be synthesized in traditional solvent-based chemistry.