Linearly arranged metal atoms that are embedded in discrete molecules have fascinated scientists across various disciplines for decades; this is attributed to their potential use in microelectronic devices on a submicroscopic scale. Luminescent oligonuclear Group 11 metal complexes are of particular interest for applications in molecular light-emitting devices. Herein, we describe the synthesis and characterization of a rare, homoleptic, and neutral linearly arranged tetranuclear Cu(I) complex that is helically bent, thus representing a molecular coil in the solid state. This tetracuprous arrangement dimerizes into a unique octanuclear assembly bearing a linear array of six Cu(I) centers with two additional bridging cuprous ions that constitute a central pseudo-rhombic Cu(I) 4 cluster. The crystal structure determinations of both complexes reveal close d(10) ⋅⋅⋅d(10) contacts between all cuprous ions that are adjacent to each other. The dynamic behavior in solution, DFT calculations, and the luminescence properties of these remarkable complexes are also discussed.
We herein report the synthesis and characterization of a terphenyl-substituted Sn(II) allyl compound featuring an η(3) coordination mode in solution and in the solid state. Two examples for the interesting reactivity of the allyl Sn(II) molecule are presented: Reactions with terminal alkynes result in the formation of tricyclic compounds by CC bond formation and the dimerization of two Sn moieties whereas the reaction with benzonitrile leads to a sixteen-membered ring system through CH activation.
(tripSn) (trip = 2,4,6-i-PrCH) reacts with Mg(i) reductants (LMg) (L = HC[C(Me)N(dipp)]) and (L'Mg) (L' = HC[C(Me)N(mes)]) with Sn-C bond cleavage and formation of the novel metalloid tin cluster Sntrip 1 or elemental tin. 1, which contains Sn atoms in the formal oxidation states 0, +I and +II, and the side products LMgtrip (2) and L'Mgtrip (3) were characterized spectroscopically and by single crystal X-ray diffraction.
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