The complexation of different simple anions (F-, Cl-, BF4- and ClO4-) with a neutral cryptand, with neutral B-N dipoles as functional units, and modifications thereof has been studied using ab initio Hartree-Fock calculations. F- is the most strongly preferred anion for all cryptand versions, except for the largest cavity cryptand for which Cl- is preferred. The formed complexes in general show very low lithium ion affinities, much lower than those for anions such as PF6- and TFSI (by up to 50%). The lowest lithium affinity is obtained for the combination of the smallest cryptand and the F- anion. Implications of using these cryptands in polymer electrolytes are discussed. (C) 2003 Elsevier Science Ltd. All rights reserved.