Ion formation pathways of crown ether-fullerene conjugates in the gas phase.

The ion formation of crown ether-[60]fullerene conjugates of the type (crown - H)-C60-H with crown = 12cr4, 15cr5 and 18cr6 has been studied with matrix-assisted laser desorption/ionisation (MALDI) and electrospray ionisation mass spectrometry (ESI MS). In total five different ways of ion formation are presented, including metalation (MALDI, ESI), protonation and oxidation (both in MALDI) in the positive-ion mode and deprotonation (MALDI, ESI) and reduction (MALDI) in the negative-ion mode. In line with thermochemistry, the deprotonation and electron transfer processes involve the C60 moiety as the charge-carrying entity, while protonation and metalation occur at the crown ether.

Polyoxopalladates encapsulating 8-coordinated metal ions, [MO8Pd(II)12L8]n- (M = Sc3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Lu3+; L = PhAsO3(2-), PhPO3(2-), SeO3(2-)).

A total of 16 discrete polyoxopalladates(II) [MO(8)Pd(II)(12)L(8)](n-), with a metal ion M encapsulated in a cuboid-shaped {Pd(12)O(8)L(8)} cage, have been synthesized: the phenylarsonate-capped series (1) L = PhAsO(3)(2-), M = Sc(3+) (ScPhAs), Mn(2+) (MnPhAs), Fe(3+) (FePhAs), Co(2+) (CoPhAs), Ni(2+) (NiPhAs), Cu(2+) (CuPhAs), Zn(2+) (ZnPhAs); the phenylphosphonate-capped series: (2) L = PhPO(3)(2-), M = Cu(2+) (CuPhP), Zn(2+) (ZnPhP); and the selenite-capped series (3) L = SeO(3)(2-), M = Mn(2+) (MnSe), Fe(3+) (FeSe), Co(2+) (CoSe), Ni(2+) (NiSe), Cu(2+), (CuSe), Zn(2+) (ZnSe), Lu(3+) (LuSe)). The polyanions were prepared in one-pot reactions in aqueous solution of [Pd(3)(CH(3)COO)(6)] with an appropriate salt of the metal ion M, as well as PhAsO(3)H(2), PhPO(3)H(2), and SeO(2), respectively, and then isolated as hydrated sodium salts Na(n)[MO(8)Pd(II)(12)L(8)]·yH(2)O (y = 10-37). The compounds were characterized in the solid state by IR spectroscopy, single-crystal XRD, elemental and thermogravimetric analyses.