This Chapter reviews the literature reported during 2006 in the field of Supramolecular Chemistry. The review focuses on the design, synthesis and self-assembly of metal-based units leading to the construction of metallosupramolecular architectures. Highlights Highlights include the synthesis and structural characterisation of Chiral Borromeates, knots that are characterized by the Brunnian link, 4 the formation of 1D luminescent inorganic micro-and nano-wires directed by Pt II Á Á ÁPt II

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... ctions, 15 and the self assembly and crystallization of giant polyoxometalates, comprising both wheel shaped and hollow, spherical structures. These are combined together leading to a single mesoscopic molecule. 64 The direct crystallographic observation of the in situ generated Cp 0 Mn(CO) 2 (Cp 0 = methylcyclopentadienyl) 16 electron unsaturated complex by photodissociation of Cp 0 Mn(CO) 3 in a self assembled coordination cage has been achieved and shows that the geometry of an unsaturated 16 electron transition metal centre adopts a pyramidal geometry. 68 Metallomacrocycles A new ditopic triphenylamine-based bis(terpyridine) ligand 4,4 0 -bis(2,2 0 :6 0 ,2 00 -terpyridinyl)triphenylamine (L1) possessing the disubstituted triphenylamine unit as an angle-control element, which can form hexagonal metallomacrocycles, has been synthesized. This ligand system is found to form a unique hexagonal metallomacrocycle family [Fe 6 (L1) 6 (PF 6 ) 12 ] and [Zn 6 (L1) 6 (BF 4 ) 12 ], utilizing terpyridine-metal(II)terpyridine connectivity. The structures of the ligand and the corresponding