The heterobimetallic 1D-polymeric alkali metal/lanthanoid [AMLn(Q)(4)](n) [Q = OQ (8-quinolinolate): AM = Li, Ln = Tb, Ho, Er; AM = K, Ln = Er; Q = MQ (2-methyl-8-quinolinolate): AM = Rb; Ln = Tb, Er] complexes were obtained after rearrangement reactions between AM(Q) and Ln(Q)(3) in a 1,2,4,5-tetramethylbenzene flux at elevated temperatures. In these compounds, the eight-coordinate lanthanoid ion is surrounded by four (O, N) chelating Q ligands, which bridge to the adjacent alkali metal through their oxygen atoms to form the linear polymers. Dimeric [Cs(2)(MQ)(2)(HMQ)(2)] was obtained from an attempt to prepare [CsEr(MQ)(4)](n), and the caesium atoms are each ligated by one terminal HMQ and one chelating-bridging MQ ligand. In addition, the chelating-bridging ligands in [Cs(2)(MQ)(2)(HMQ)(2)] and in the rubidium derivatives [RbLn(MQ)(4)](n) (Ln = Tb, Er) exhibit bonding of the pi-electron system to coordination saturate the large ionic alkali metal ion. The reaction of Yb(MQ)(3) in the presence of K(2)C(2)O(4)center dot H(2)O afforded the monomeric heterobimetallic [KYb(2)(MQ)(7)] complex in which the three metal atoms are arranged in a triangular fashion. They are surrounded by seven MQ ligands, which display the previously encountered chelating (O, N) and the chelating-bridging mu-kappa(2)(N,O):kappa(1)(O) and mu(3)-kappa(2)(N,O):kappa(1)(O):kappa(1)(O) ligation modes. Heating K(OQ) in 1,2,3,4-tetrachlorobenzene gave crystals of 8-hydroxyquinolinium chloride. The structure of [Na(4)(OQ)(4)(H(2)O)(8)](n), obtained by neutralisation, has sodium ions coordinated by one chelating OQ and four aqua ligands, the latter bridge to adjacent sodium ions to give a double stranded 2D-polymer.