Shape‐Complementary Multicomponent Assembly of Low‐Symmetry Co(III)Salphen‐Based Coordination Cages

Author:

Zhang Bo1,Lee Haeri2,Holstein Julian J.1,Clever Guido H.1ORCID

Affiliation:

1. Department of Chemistry and Chemical Biology TU Dortmund University Otto-Hahn-Strasse 6 44227 Dortmund Germany

2. Department of Chemistry Hannam University 1646 Yuseong-daero, Yuseong-gu Daejeon 34054 Republic of Korea

Abstract

AbstractWhile metal‐mediated self‐assembly is a popular technique to construct discrete nanosized objects, highly symmetric structures, built from one type of ligand at a time, are dominating reported systems. The tailored integration of a set of different ligands requires sophisticated approaches to avoid narcissistic separation or formation of statistical mixtures. Here, we demonstrate how the combination of three structure‐guiding effects (metal‐templated macrocyclization, additional bridging ligands and shape‐complementarity) based on Co(III)salphen metal nodes allows for a rational and high‐yielding synthesis of structurally complex, lantern‐shaped cages with up to four differentiable bridges. Three new heteroleptic coordination cages based on dinuclear Co(III)salphen macrocycles were synthesized in a one‐pot reaction approach and fully characterized, including single crystal X‐ray analyses. One cage groups two of the same ligands, another two different ligands around a symmetric Co2‐bis‐salphen ring. In the most complex structure, this ring is unsymmetric, rendering all four connections between the two metal centers distinguishable. While heteroleptic assembly around Pd(II) nodes has been shown to be dynamic, beneficial for cage‐to‐cage transformations, assembly cascades and adaptive systems, the herein introduced cages based on kinetically more inert Co(III)salphen will be advantageous for applications in enzyme‐like catalysis and molecular machinery that require enhanced structural and chemical stability.

Funder

Deutsche Forschungsgemeinschaft

H2020 European Research Council

National Research Foundation of Korea

Deutsches Elektronen-Synchrotron

Publisher

Wiley

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