Trapping White Phosphorus within a Purely Organic Molecular Container Produced by Imine Condensation

Abstract

Three tetrahedral organic cages have been obtained by condensing at riamino linker with as et of three ostensibly analogous triformyl precursors.D espite the large number of imine bonds formed, the corresponding cages were obtained in exceptionally high yields.Both theory and experimental results demonstrate that intramolecular CH···p interactions within all of the cage frameworks play an important role in abetting the condensations and contributing to the near-quantitative synthetic yields.T he three cages of this study exhibit high thermodynamic and kinetic stability.Avariety of small neutral guest molecules with complementary sizes and geometries may be used as templates in the cage forming reactions.Among the guests that may be used in this way is white phosphorus (P 4 ), whose inherent reactivity towards oxygen is almost fully attenuated when bound within one of the cages.

Stabilization of Dynamic Covalent Architectures by Multivalence

“…A few years later, our group [39] obtained a series of tetrahedral cages 3 and 4 in a [4 + 4] manner, by condensing the trisamino linker A2 and each of a set of ostensibly analogous triformyl precursors namely F2 and F3 in chloroform (Figure 5). The yields of these cages are remarkably high, ranging from 90 % to 99 % determined by using internal standard in the 1 H NMR samples.…”

Molecular Cages Self‐Assembled by Imine Condensation in Water

“…More recently,i th as been observed [10] that multivalence could help to solidify the self-assembled molecular entities. That is,e ven though each of the dynamic bonds including imine is rather labile and apt to hydrolyze,the self-assembled molecules might become rather kinetically inert, when each of the building blocks is connected with each other via multiple linkages.Simultaneous cleavage of multiple bonds is obviously much more difficult than breaking asingle dynamic bond.…”

Cucurbitimines – imine cages with concave walls

“…[1][2][3][4][5][6] Although a few examples of boronic ester cages, or those based on disulphide formation or other DCC reactions are known, [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] no doubt, the vast majority of shape-persistent organic cages is relying on the use of multiple imine condensation reactions, 1 which bear the advantage to be transformed further to convert these to chemically robust cages, [27][28][29][30][31] which is for the other type of DCC reactions difficult or even impossible. 32 Among those imine cages, shapes, such as trigonal prisms, [33][34][35] tetrahedra, [36][37][38][39] truncated tetrahedra, 40,41 cubes, [42][43][44][45][46] tetrapods,…”