Different Modes of Anion Response Cause Circulatory Phase Transfer of a Coordination Cage with Controlled Directionality

Abstract

Controlled directional transport of molecules is essential to complex natural systems, from cellular transport up to organismal circulatory systems. In contrast to these natural systems, synthetic systems that enable transport of molecules between several spatial locations on the macroscopic scale, when external stimuli are applied, remain to be explored. Now, the transfer of a supramolecular cage is reported with controlled directionality between three phases, based on a cage that responds reversibly in two distinct ways to different anions. Notably, circulatory phase transfer of the cage was demonstrated based on a system where the three layers of solvent are arranged within a circular track. The direction of circulation between solvent phases depended upon the order of addition of anions.

Synthesis of Highly Functionalizable Symmetrically and Unsymmetrically Substituted Triarylboranes from Bench‐Stable Boron Precursors

“…Overview of reported follow-up reactions, to which the BXyl 3 moiety (BAr 3 or BAr 2 Ar') is tolerant, and selected functional groups that have been attached. Examples of each path are given in the following references: a, [26][27][28][29][30] b, [27,[29][30][31][32][33] c, [34,35] d, [36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51] e, [52][53][54][55][56][57] f, [42,[58][59][60][61][62] g, [63][64][65][66][67] and h. [68][69][70][71]…”

“… Overview of reported follow‐up reactions, to which the BXyl 3 moiety (BAr 3 or BAr 2 Ar’) is tolerant, and selected functional groups that have been attached. Examples of each path are given in the following references: a,[ 26 , 27 , 28 , 29 , 30 ] b,[ 27 , 29 , 30 , 31 , 32 , 33 ] c,[ 34 , 35 ] d,[ 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 ] e,[ 52 , 53 , 54 , 55 , 56 , 57 ] f,[ 42 , 58 , 59 , 60 , 61 , 62 ] g,[ 63 , 64 , 65 , 66 , 67 ] and h.[ 68 , …”

“…Even deprotonation or lithium‐halide exchange reactions can be employed to functionalize triarylboranes due to their high tolerance towards different reaction conditions (Figure 2 d). [ 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 ] By reaction with different electrophiles, various functional groups, for example, CO 2 H or COH, can be introduced. In general, introduction of electron donating or accepting groups has a strong effect on the optoelectronic properties of triarylboranes.…”

Functional Material Systems Based on Soft Cages

“…Mihara et al. reported the realization of cross‐phase transfer of molecular cages 26 in a three‐phase system by changing the type of anions [43] . A new type of FeII 4 L 4 tetrahedral cage containing tricoordinated boron atoms at the center of each face was synthesized.…”

Emerging Spacers‐Based Ligands for Supramolecular Coordination Complexes

“…Nitschke and co‐workers outlined the synthesis of a stimuli responsive cationic Fe(II) tetrahedral cage [ 32 ] 8+ having four triarylborane at the center of each face through a multi‐component self‐assembly approach [67] . The cage was assembled by simple mixing of L 32a , L 32b , and Fe(II).…”