Journal Article

PUBDB-2024-05113

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Heteromeric Completive Self-Sorting in Coordination Cage Systems

Benchimol, E.Extern* ; Regeni, I.Extern* ; Zhang, B. ; Kabiri, M. ; Holstein, J. J.Extern* ; Clever, G. (Corresponding author)Extern*

2024
ACS Publications Washington, DC

This record in other databases:        

Please use a persistent id in citations: doi:10.1021/jacs.3c14168  doi:10.3204/PUBDB-2024-05113

Abstract: 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$_2$A$_2$B$_2$ and Pd$_2$A$_2$C$_2$, 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$_2$B$_2$C$_2$ 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$_2$AB$_2$C cage to heteromeric completive self-sorting to give Pd$_2$A$_2$B$_2$ and Pd$_2$A$_2$C$_2$ 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$_2$A$_2$B$_2$ or occupy two cis-edges in Pd$_2$A$_2$C$_2$ or only a single edge in Pd$_2$AB$_2$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.

Note: Copyright @ACS

---

Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. FS-Proposal: I-20211437 (I-20211437) (I-20211437)
3. FS-Proposal: I-20210921 (I-20210921) (I-20210921)
4. GRK 2376 - GRK 2376: Umgrenzungsgesteuerte Chemie (331085229) (331085229)
5. DFG project 390677874 - EXC 2033: RESOLV (Ruhr Explores Solvation) (390677874) (390677874)

Experiment(s):

1. PETRA Beamline P11 (PETRA III)

Appears in the scientific report 2024

---

Database coverage:
; ; BIOSIS Previews ; Biological Abstracts ; Chemical Reactions ; Clarivate Analytics Master Journal List ; Current Contents - Life Sciences ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; Essential Science Indicators ; IF >= 15 ; Index Chemicus ; JCR ; Nationallizenz ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

---