Lanthanide, main group, and transition metal ion templates provide different polynuclear cages from [M(L)] (M=Ni, Mn; (L)2−=CH2[CH2N=C(CH3)COO−]2). Templating with lanthanum results in a 12‐coordinate LaIII ion encapsulated by six [Ni(L)] units, whereas with sodium four Na+ ions are trapped inside a tricapped trigonal prismatic [{Ni(L)}9] cage. With manganese, an octahedrally coordinated MnII ion is surrounded by six [Mn(L)] fragments in a twisted trigonal‐prismatic configuration (see picture).

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In the infrared spectra of mono- and di-nitrate esters of the l,4;3,6-dianhydrides of d-mannitol, d-glucitol, and l-iditol in benzene solution (0.04 M in nitrato groups), the frequencies of the va(NO2) and v(ON) bands (singlets) were 1 645 ± 3 and 843 ± 3 cm−1, respectively, whereas the vs(NO2) band occurred at frequencies characteristic of either an endo (1 282 ± 1 cm−1) or an exo (1 274 ± 1 cm−1) configuration of the nitrato group; the ratios of the band areas were 1.5:1.0:1.0, respectively.The stereospecific frequency of the vs(NO2) band was attributed to non-bonded intramolecular interaction between the nitrato group and vicinal oxy groups on the basis of the spectra run in a series of solvents and the molecular conformations determined by X-ray crystallography. This new stereochemical probe permitted the assignment of the structure, configuration, and conformation in a series of nitrate esters.

Template in Form von Lanthanoid‐, Hauptgruppen‐ und Nebengruppenmetallionen ermöglichen die Bildung verschiedener mehrkerniger Käfige aus [M(L)] (M=Ni, Mn; (L)2−=CH2[CH2N=C(CH3)COO−]2). Mit Lanthan führt die Templatsynthese zu einem ikosaedrisch koordinierten LaIII‐Ion, das von sechs [Ni(L)]‐Einheiten eingeschlossen wird. Mit Natrium hingegen entsteht ein dreifach überdachter, prismatischer [{Ni(L)}9]‐Käfig, der vier Na+‐Ionen im Innern enthält. Mit Mangan schließlich konnte ein von sechs [Mn(L)]‐Fragmenten koordiniertes MnII‐Ion erhalten werden, das in eine verzerrte, trigonal‐prismatische Anordnung eingebettet ist (siehe Bild).

The assembly of [Cd(L 1 )] Ϫ {[L 1 ] 3Ϫ ϭ N[CH 2 CH 2 Nϭ C(CH 3 )COO Ϫ ] 3 } into the tetranuclear cluster {[Cd(L 1 )]Na-(H 2 O) 2 } 2 in the presence of Na ϩ is mediated by Na ϩ -carboxylate interactions; in contrast In 3ϩ and Fe 3ϩ induce the partial hydrolysis of [L 1 ] 3Ϫ to afford the complexes [In(L 2 )Cl] and {[Fe(L 2 )] 2 O} Der Effekt partieller Hydrolyse beim Wechsel der Art der intermolekularen Bindung zwischen Metall-Komplexen Inhaltsübersicht. Die Umwandlung von [Cd(L 1 )] Ϫ ([L 1 ] 3Ϫ ϭ N[CH 2 CH 2 NϭC(CH 3 )COOϪ] 3 ) in den vierkernigen Cluster {[Cd(L 1 )]Na(H 2 O) 2 } 2 in Anwesenheit von Na ϩ wird durch Na ϩ -Carboxylat-Wechselwirkungen vermittelt. Im Gegensatz hierzu Polymers and oligomers formed from metal complexes are currently the subject of much interest due to the possibility that such compounds may exhibit catalytic, magnetic, optical and conductivity properties [1]. Several strategies have been developed towards the assembly of such aggregates [2Ϫ5]. One such strategy has involved the incorporation of groups onto the ligand periphery that are capable of forming intermolecular hydrogen-bonds with other substrate molecules [3]. Another approach has been to chelate metal ions with polychelate ligands that contain carboxylate ligands, facilitating the formation of aggregates via induzieren In 3ϩ und Fe 3ϩ die partielle Hydrolyse von [L 1 ] 3Ϫ unter Bildung der Komplexe [In(L 2 )Cl] und {[Fe(L 2 )] 2 O} ([L 2 ] 2Ϫ ϭ N[CH 2 CH 2 NH 2 ][CH 2 CH 2 NϭC(CH 3 )COOϪ] 2 ), die über intermolekulare Wasserstoffbrücken-Bindungen aggregieren.interaction with hard metal cations [4,5]. We have become interested in the possibility of being able to 'switch' the mode of complex aggregation to that of hydrogen-bonding through the partial hydrolysis of one arm of [L 1 ] 3Ϫ to give the hexadentate ligand [L 2 ] 2Ϫ . There have been reports of the partial hydrolysis of Schiff-base ligands upon complexation with a metal centre [6Ϫ8] either to alleviate unfavourable steric interactions within the complex [7] or to form a ligand of improved donor ability [8]. Therefore, our approach to the synthesis of complexes of [L 2 ] 2Ϫ has been to investigate the reaction of [L 1 ] 3Ϫ with a range of metal ions of differing size and co-ordination requirements. The preliminary studies reported herein have utilised the metal ions In 3ϩ , Cd 2ϩ and Fe 3ϩ .Reaction of [L 1 ]Na 3 · 3H 2 O 1) with one molar equivalent of InCl 3 in MeOH results in the precipitation of irregular block shaped crystals. Single crystal X-ray diffraction re-1) [L 1 ]Na 3 · 3H 2 O is prepared via the Schiff-base condensation of tris(2-aminoethylamine) with three molar equivalents of sodium pyruvate in MeOH. Satisfactory elemental analytical data, mass spectra and infrared spectra were obtained for all compounds reported. Satisfactory 1 H and 13 C NMR spectra were obtained for [L 1 ]Na 3 · 3H 2 O, 1 and 2.