Boronate Covalent and Hybrid Organic Frameworks Featuring P^III and P=O Lewis Base Sites

Abstract

We have demonstrated that the general approach to phosphine coordination materials, mostly developed for MOF families, can be successfully extended to Covalent Organic Frameworks. Consequently,w eh ave obtained as eries of COFs comprising both Lewis acid boron and Lewis base P III /P=Os ites. These bifunctional COFs showed significant gas sorption ability and can be easily functionalized with metal atoms using both post-synthetic and bottom-up approaches. The DFT calculations on framework-guest interactions revealed that the behavior of adjacent boron and P III /P=Oc enters is reminiscent of that found in Frustrated Lewis Pairs.

Design of aD3h-symmetry prismatic tris-(ferrocene-1,1′-diyl) molecular cage bearing boronate ester linkages

“…Boronic esters are among the most widely used linkage motifs in the synthesis of highly organized structures, e.g., covalent organic frameworks (COFs). [1][2][3][4][5] In fact, some of the first COFs were synthesized by polycondensation of diboronic acids and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP). 6 The usefulness of boronic ester linkages stems from their D 2h symmetry and the thermodynamically favoured esterification reaction.…”