Abstract
AbstractA family of ditopic hexadentate ligands based on the parent compound 2,6‐bis(6‐(pyrazol‐1‐yl)pyridin‐2‐yl)‐1,5‐dihydrobenzo[1,2‐d:4,5‐d’]diimidazole (L) was developed and synthesized by using a straightforward condensation reaction, which forms the interlinking central benzo[1,2‐d:4,5‐d’]diimidazole bridge in the ligand backbone. The two secondary amine groups of the benzodiimidazole unit tautomerize and allow the formation of two tauto‐conformers, which upon treatment with metal salts forms different isomeric coordination complexes. Here we report six new derivatives (1–6) that can tautomerize (varying the pyrazolylpyridine part) and 14 derivatives (7–13) with different alkyl and benzyl substitution on secondary amino groups (of L) that prevent the tautomerization. This way, it is possible to study the properties of isomeric coordination complexes and their intrinsic cooperativity by the example of [2x2] grid complexes in the future. A [2x2] Zn4 complex of the ligand L was synthesized and structurally characterized.
Highlights
Ditopic ligands are of continuing interest to the covalent integration of metal ions into molecular metal complexes.[1]
The intrinsic electronic and steric properties of ligand L can be adapted, which is apparent from the synthetic procedure shown in Scheme 1
A family of ditopic hexadentate ligands with a central dihydrobenzo-diimidazole unit based on the mother compound
Summary
Ditopic ligands are of continuing interest to the covalent integration of metal ions into molecular metal complexes.[1] Such ligands with at least two metal-binding domains can be used to synthesize homo and hetero multi-metallic complexes such as metal-containing supramolecular and macromolecular species (polymers, dendrimers, molecular wires) and oligonuclear grid type metal complexes.[2,3,4,5] If the coordination sites of [b] Dr O. Fuhr Karlsruhe Nano Micro Facility (KNMF), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany [c] Prof. Kappes Institute of Physical Chemistry (IPC), Karlsruhe Institute of Technology (KIT), Fritz-Haber Weg 2, G 30.44, 76131 Karlsruhe, Germany [d] Prof. M. Ruben Institute of Quantum Materials and Technologies (IQMT) Karlsruhe Institute of Technology (KIT) Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany [e] Prof. M. Ruben Centre Européen de Sciences Quantiques (CESQ) in the Institut de Science et d’Ingénierie Supramoléculaires (ISIS), 8 allée Gaspard Monge, BP 70028, 67083 Strasbourg Cedex France
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