TY  - JOUR
AU  - Benchimol, Elie
AU  - Regeni, Irene
AU  - Zhang, Bo
AU  - Kabiri, Michele
AU  - Holstein, Julian J.
AU  - Clever, Guido
TI  - Heteromeric Completive Self-Sorting in Coordination Cage Systems
JO  - Journal of the American Chemical Society
VL  - 146
IS  - 10
SN  - 0002-7863
CY  - Washington, DC
PB  - ACS Publications
M1  - PUBDB-2024-05113
SP  - 6905-6911
PY  - 2024
N1  - Copyright @ACS 
AB  - Heteroleptic coordination cages, nonstatistically assembled from a set of matching ligands, can be obtained by mixing individual components or via cage-to-cage transformations from homoleptic precursors. Based on the latter approach, we here describe a new level of self-sorting in coordination cage systems, namely, ‘heteromeric completive self-sorting’. Here, two heteroleptic assemblies of type Pd<sub>2</sub>A<sub>2</sub>B<sub>2</sub> and Pd<sub>2</sub>A<sub>2</sub>C<sub>2</sub>, sharing one common ligand component A but differing in the other, are shown to coexist in solution. This level of self-sorting can be reached either from a statistical mixture of assemblies based on some ligands B and C or, alternatively, following a first step of integrative self-sorting giving a distinct Pd<sub>2</sub>B<sub>2</sub>C<sub>2</sub> intermediate. While subtle enthalpic factors dictate the outcome of the self-sorting, we found that it is controllable. From a unique set of three ligands, we demonstrate the transition from strict integrative self-sorting forming a Pd<sub>2</sub>AB<sub>2</sub>C cage to heteromeric completive self-sorting to give Pd<sub>2</sub>A<sub>2</sub>B<sub>2</sub> and Pd<sub>2</sub>A<sub>2</sub>C<sub>2</sub> by variation of the ligand ratio. Cage-to-cage transformations were followed by NMR and MS experiments. Single crystal X-ray structures for three new heteroleptic cages were obtained, impressively highlighting the versatility of ligand A to either form a π-stacked trans-figure-of-eight arrangement in Pd<sub>2</sub>A<sub>2</sub>B<sub>2</sub> or occupy two cis-edges in Pd<sub>2</sub>A<sub>2</sub>C<sub>2</sub> or only a single edge in Pd<sub>2</sub>AB<sub>2</sub>C. This study paves the way toward the control of heteroleptic cage populations in a systems chemistry context with emerging features such as chemical information processing, adaptive guest selectivity, or stimuli-responsive catalytic action.
LB  - PUB:(DE-HGF)16
C6  - pmid:38423558
UR  - <Go to ISI:>//WOS:001179247700001
DO  - DOI:10.1021/jacs.3c14168
UR  - https://bib-pubdb1.desy.de/record/611899
ER  -