Noncooperative guest binding by metal-free [2 + 2] Schiff-base macrocycles
Salphen-based [ n + n ] macrocycles have been widely explored for their unique chemical and topological properties following metal ion coordination. Despite having vastly different reactivity than their coordinated counterparts, fewer studies have focused on metal-free salphen macrocycles. We invest...
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Published in | Organic & biomolecular chemistry Vol. 2; no. 42; pp. 8259 - 8268 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
CAMBRIDGE
Royal Soc Chemistry
02.11.2022
Royal Society of Chemistry |
Subjects | |
Online Access | Get full text |
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Summary: | Salphen-based [
n
+
n
] macrocycles have been widely explored for their unique chemical and topological properties following metal ion coordination. Despite having vastly different reactivity than their coordinated counterparts, fewer studies have focused on metal-free salphen macrocycles. We investigated the binding of [2 + 2] Schiff-base macrocycle host
3
, which contains a central 18-crown-6-like cavity and two N
2
O
2
moieties. This macrocycle strongly binds to spherical cationic guests (
K
11
10
3
-10
4
M
−1
, DCM/MeCN). The most robust binding was shown for K
+
and Na
+
, followed by Li
+
and Rb
+
. More sterically demanding cationic guests like dibenzylammonium (
DBA
+
) showed almost no binding. The binding pocket in
3
is slightly smaller than 18-crown-6, resulting in binding outside the cavity, which provides a scaffold appropriate for 2 : 1 complexes, where two host molecules sandwich the guest. All host-guest complexes follow a 2 : 1
noncooperative
binding model, where each successive binding event is less likely than the previous, unlike coordinated versions of
3
, where most binding is 1 : 1.
Soluble [2 + 2] Schiff-base macrocycles were synthesized, characterized by single-crystal X-ray diffraction, and investigated for their ability to bind alkali metal cations. |
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Bibliography: | Electronic supplementary information (ESI) available. CCDC For ESI and crystallographic data in CIF or other electronic format see DOI 2167048 2167047 https://doi.org/10.1039/d2ob01511k and 2099766 2167051 , 2167050 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1477-0520 1477-0539 |
DOI: | 10.1039/d2ob01511k |