Novel macroheterocyclic tetraphosphines, namely, 1,1',5,5'-bis(arylene)-bis(1,5-diaza-3,7-diphosphacyclooctanes) 2-6, were obtained without the use of high-dilution techniques or any matrix by the reaction of bis(hydroxymethyl)organylphosphines with primary aromatic diamines containing two p-phenylene fragments linked by various one-atom bridges in a molecular self-assembly process. The structures of 4, 5 and 6 were investigated by X-ray crystal structure analyses. The macrocyclic cavities can be described as a truncated rhombohedral prism with side faces formed by phenylene rings and 1,5-diaza-3,7-diphosphacyclooctanes in the truncated acute angles. In the crystals of these macrocycles, solvating DMF molecules are present, and a methyl group from each of two DMF molecules penetrates the macrocyclic cavities of 4 and 5 from either side, whereas only one disordered molecule of DMF penetrates the cavity of macrocycle 6. Different types of crystal packing are observed for the P-benzyl-substituted compounds 4 and 5 and for the P-mesityl-substituted compound 6: for 4 and 5 the formation of alternating layers containing the macrocycles and the DMF molecules is observed, in which the cavities of the macrocyclic molecules form channels and the DMF molecules are located in the centers of the channels; in the crystal of 6, six molecules are arranged around the 3 axis in the fashion of a six-bladed propeller.

The novel type

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An effective strategy of P,N-containing macrocycle design is described, which is based on covalent self-assembly processes in the course of Mannich-type condensations in threecomponent systems: primary phosphine (or secondary diphosphine)-formaldehydediamine with spatially divided functional groups (or primary amine). This approach allowed the authors to obtain various types of macrocyclic phosphines, namely cage cyclophanes with a 1,5-diaza-3,7-diphosphacyclooctane fragment in the basic framework, cyclophanes with linear P,N-containing spacers, P,N-containing corands and the first P,Ncontaining cryptand with four phosphine centers.

1,5-bis(R)-3,7-bis[2-(pyridine-2Ј-yl)ethyl)-1,5-diaza-3,7-diphosphacyclooctanes 1 and 2 and their copper(I) complexes 3 and 4 were developed. The butterfly-shaped copper-iodide core and unusual P,N-chelate and P,P-bridged coordination mode of the heterocyclic ligand in the dinuclear complexes 3 and 4 were revealed. Complexes 3 895 and 4 display emission in green range of spectra, with lifetimes in a microsecond domain and quantum yields of luminescence in solidstate up to 38 %. Thermochromic effects found for the phosphorescence of 4 in solutions are ascribed to rigidochromism.