Self-assembly of novel macrocyclic aminomethylphosphines with hydrophobic intramolecular cavities.
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.
Balueva
Anna S
AS
A. E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, Kazan Scientific Center, Arbuzov str. 8, Kazan, Russian Federation, 420088.
Kuznetsov
Roman M
RM
Ignat'eva
Svetlana N
SN
Karasik
Andrey A
AA
Gubaidullin
Aidar T
AT
Litvinov
Igor A
IA
Sinyashin
Oleg G
OG
Lönnecke
Peter
P
Hey-Hawkins
Evamarie
E
D018360:Crystallography, X-Ray; D057927:Hydrophobic and Hydrophilic Interactions; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D010720:Phosphines / Q000138:chemical synthesis* / Q000737:chemistry; D016062:Porosity
D047028:Macrocyclic Compounds; D010720:Phosphines