The interaction of ferrioxamine B, FeHDFB+, through a protonated amine side chain, with various host ionophore structures to form a host-guest complex in the second coordination shell has been investigated, Host-guest association constants (K-a) in water saturated chloroform are reported for synthetic crown ethers with different cavity size and substituents (18-crown-6 and its dicyclohexano, benzo, and dibenzo derivatives; dibenzo and dicyclohexano derivatives of 24-crown-8; and dibenzo-30-crown-10). The natural ionophores valinomycin and nonactin were also found to form stable second-sphere complexes with ferrioxamine B in wet chloroform, Results are reported for both picrate and perchlorate salts of FeHDFB+. Since the protonated amine side chain of ferrioxamine B may be viewed as a substituted amine, the host-guest association constants for FeHDFB+ are compared to the interaction of Mg2+, K+, NH4+, CH3(CH2)(4)NH3+, and H1DFB+ with the same ionophores, This is the first report of nonactin complexation of this series of cations in an organic medium of low polarity and one of the few reports of valinomycin complexation. To the best of our knowledge these are the first reported stability constants for the association of (Mg2+,2pic(-)) with natural and synthetic ionophores in chloroform. K-a, values for ferrioxamine B complexation by the synthetic crown ethers are influenced by ring size and substituent, Despite significant preorganization capabilities, the large cavities of valinomycin, nonactin and benzo-30-crown-10 do not form as stable host-guest assemblies with bulky substituted amine cations such as ferrioxamine B as does cis-dicyclohexano-18-crown-6.