Oxaphosphacyclophanes Constructed from a Bis(triphenylphosphine oxide) Moiety Linked by Dioxyalkyl Chains: Synthesis and Crystal Structures

Abstract

Oxaphosphacyclophanes, a bis(triphenylphosphine oxide) moiety linked by dioxypropane, dioxybutane, dioxypentane, and dioxyhexane, were synthesized from the reaction of bis(4-hydroxyphenyl)phenylphosphine oxide and dibromoalkanes. Single-crystal X-ray diffraction analysis and exploring intermolecular interactions by using the Hirshfeld surface revealed that the butylene-linked oxaphosphacyclophane ( 2 ) had a one-dimensional (1D) supramolecular structure via CH/π interactions between the terminal phenyl group of 2 and a phenylene group of the cavities. In the packing diagram of pentylene-linked oxaphosphacyclophane ( 3 ) with antiform, one macrocycle recognized two terminal phenyl groups to form a 1D supramolecular chain via π/π interactions. The syn-form of 3 was obtained by the recrystallization from toluene and CHCl 3 . In this crystal, a toluene molecule avoid construction of a 1D chain. The antiform of hexylene-linked oxaphosphacyclophane 4 was obtained by the recrystallization from cyclohexane and CHCl 3 . Cyclohexane was captured in the cavity via CH/π interactions. Two molecules of 4 with the syn-form recognized each other to construct a dimeric structure via CH/π interactions.

First Example of Cage P4N4-Macrocycle Copper Complexes with Intracavity Location of Unusual Cu2I Fragments

“…The second site is a hydrophobic intramolecular cavity bounded by phenylene fragments which is suitable for host–guest interactions with small organic molecules or for encapsulation of a metal-containing fragment connected with a phosphorus atom. This explains why phosphorus-containing cyclophanes could be regarded to be a promising scaffold for tailor-made transition metal complexes which may be of interest both for homogeneous catalysis and for the creation of novel recognition systems and molecular materials [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 ].…”