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Large, heterometallic coordination cages based on ditopic metallo-ligands with 3-pyridyl donor groups.

ABSTRACT: Ditopic N-donor ligands with terminal 4-pyridyl groups are omnipresent in coordination-based self-assembly. The utilization of ligands with 3-pyridyl donor groups is significantly less common, because the intrinsic conformational flexibility of these ligands tends to favor the formation of small aggregates. Here, we show that large Pd6L1212+ cages can be obtained by reaction of Pd(ii) salts with metallo-ligands L bearing terminal 3-pyridyl groups. The easy-to-access metallo-ligands contain an Fe(ii) clathrochelate core. These sterically demanding clathrochelate complexes prevent the formation of smaller aggregates, which is observed for less bulky analogous building blocks. The cages were shown to bind BF4- and BPh4- anions in aqueous solvent mixtures, whilst the lateral size of the clathrochelate significantly affects their guest encapsulation behavior.

SUBMITTER: Wise MD

PROVIDER: S-EPMC5811078 | biostudies-literature | 2015 Feb

REPOSITORIES: biostudies-literature

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Large, heterometallic coordination cages based on ditopic metallo-ligands with 3-pyridyl donor groups.

Wise Matthew D MD Holstein Julian J JJ Pattison Philip P Besnard Celine C Solari Euro E Scopelliti Rosario R Bricogne Gerard G Severin Kay K

Chemical science 20141111 2

Ditopic N-donor ligands with terminal 4-pyridyl groups are omnipresent in coordination-based self-assembly. The utilization of ligands with 3-pyridyl donor groups is significantly less common, because the intrinsic conformational flexibility of these ligands tends to favor the formation of small aggregates. Here, we show that large Pd6L1212+ cages can be obtained by reaction of Pd(ii) salts with metallo-ligands L bearing terminal 3-pyridyl groups. The easy-to-acc ...[more]

PMID: 29560187

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Project description:In recent studies, porphyrin derivatives have been frequently used as building blocks for the fabrication of metal-organic coordination networks (MOCNs) on metal surfaces under ultrahigh vacuum conditions (UHV). The porphyrin core can host a variety of 3d transition metals, which are usually incorporated in solution. However, the replacement of a pre-existing metal atom in the porphyrin core by a different metallic species has been rarely reported under UHV. Herein, we studied the influence of cyanophenyl and pyridyl functional endgroups in the self-assembly of structurally different porphyrin-based MOCNs by the deposition of Fe atoms on tetracyanophenyl (Co-TCNPP) and tetrapyridyl-functionalized (Zn-TPPyP) porphyrins on Au(111) by means of scanning tunneling microscopy (STM). A comparative analysis of the influence of the cyano and pyridyl endgroups on the formation of different in-plane coordination motifs is performed. Each porphyrin derivative formed two structurally different Fe-coordinated MOCNs stabilized by three- and fourfold in-plane coordination nodes, respectively. Interestingly, the codeposited Fe atoms did not only bind to the functional endgroups but also reacted with the porphyrin core of the Zn-substituted porphyrin (Zn-TPyP), i.e., an atom exchange reaction took place in the porphyrin core where the codeposited Fe atoms replaced the Zn atoms. This was evidenced by the appearance of molecules with an enhanced (centered) STM contrast compared with the appearance of Zn-TPyP, which suggested the formation of a new molecular species, i.e., Fe-TPPyP. Furthermore, the porphyrin core of the Co-substituted porphyrin (Co-TCNPP) displayed an off-centered STM contrast after the deposition of Fe atoms, which was attributed to the binding of the Fe atoms on the top site of the Co-substituted porphyrin core. In summary, the deposition of metal atoms onto organic layers can steer the formation of structurally different MOCNs and may replace pre-existing metal atoms contained in the porphyrin core.

Dataset Information

Large, heterometallic coordination cages based on ditopic metallo-ligands with 3-pyridyl donor groups.

Publications

Large, heterometallic coordination cages based on ditopic metallo-ligands with 3-pyridyl donor groups.

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