Dedication: One of Alan Sargeson’s great abilities was to seek out knowledge on topics of which he was not the master from those people with the expertise. This led occasionally to publications with a ‘cricket team’ of authors but with a rich brew of information, often international. Alan also insisted that all authors were equal since, without any one, the paper would not be what it was. Hence, he endeavoured to pursue the policy, difficult to maintain over a period where an obsession with absurdities such as the order of authors and point-scoring based on meaningless publication indices became so important in the maintenance of research, of listing authors simply in alphabetical order. In describing work begun while he was still with us, we have attempted to adhere to his principles.
Analysis of a body of crystallographic information concerning metal(ii) and metal(iii) complexes of macrobicyclic hexamine ligands and some of their derivatives provides evidence for the action of a variety of intermolecular forces within the lattices. Hydrogen bonding is universal and its forms depend strongly upon the oxidation state and the particular nature of the metal ion bound to the macrobicycle. The introduction of both aliphatic and aromatic substituents leads to lattices in which these substituents associate, although, in the case of aromatic substituents, this is not necessarily a consequence of ‘π-stacking’, despite the fact that the aromatic ring planes form parallel arrays. At least in the case of CoIII, stable enantiomers of the complexes can be obtained, and in {Δ-(+)589-[Co{(NH3)(CH3)sar}]}2Cl2(C6(CO2)6)·26H2O (sar = 3,6,10,13,16,19-hexa-azabicyclo[6.6.6]icosane), the benzene hexacarboxylate anion adopts a chiral conformation in the presence of the optically active cation.
We have performed an in-depth correlation-crystal-field (CCF) analysis of the energy-level structures in 10 Nd3+(4f3) crystal systems: NdF3, Nd2Te4O11, NdVO4, NdPO4, Nd3+:LiYF4, Nd3+:LaVO4, Nd3+:LaCl3, Nd3+:BaY2F8, Nd3+:YAlO3 and Nd3+:LuA1O3. A model Hamiltonian employing 20 free-ion parameters, appropriate one-electron crystal-field interaction parameters and also selected two-particle CCF interaction parameters was diagonalized within the complete 364 SLJMJ basis set of the 4f3 electronic configuration. Inclusion of the fourth-rank g2(4), g10A(4) and g10B(4) CCF operators in the phenomenological energy-level fits yields an overall improved agreement between calculated and empirical energy levels besides eliminating major discrepancies between calculated and observed crystal-field splittings within the anomalous 2H(2)11/2 multiplet of Nd3+ ion. The fits are also in qualitative agreement with the ab initio calculations of CCF effects for lanthanide ions.
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