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. 2023 Aug 9;3(5):305-311.
doi: 10.1021/acsorginorgau.3c00021. eCollection 2023 Oct 4.

Binuclear Complexes Supported by a Tetrapyridyl Ligand with a Bending Anthraquinodimethane Linker

Takahiro Iwamoto  1 , Yuta Sotome  1 , Youichi Ishii  1
Affiliations

Binuclear Complexes Supported by a Tetrapyridyl Ligand with a Bending Anthraquinodimethane Linker

Takahiro Iwamoto et al. ACS Org Inorg Au. .

Abstract

A tetrapyridyl ligand with a bending anthraquinodimethane linker has been synthesized, and its complexation with coinage metals has been examined. The treatment of the ligand with Ag(I) and Au(I) cations afforded binuclear complexes, wherein the two metal centers were in close proximity to the inside space of the ligand. X-ray analyses corroborated with theoretical calculations indicated that the ligand has reasonable flexibility toward a bending deformation of the linker moiety to provide a ligand pocket suitable for the proximal binuclear complexes, even though such deformations accompany a non-negligible amount of energetic cost. On the other hand, treatment with 2 equiv of Cu(I) salt afforded a binuclear complex, in which both copper atoms were coordinated at the periphery of the ligand.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Ligand pockets for bimetallic complexes containing two metals in close proximity.
Figure 2
Figure 2
Solid-state structure of ligand 1 with thermal ellipsoids at 50% probability. Hydrogen atoms are omitted for clarity. C: gray and N: purple.
Figure 3
Figure 3
Complexation of ligand 1 with AgOTf.
Figure 4
Figure 4
Solid-state structure of (a) complex 2(OCMe2) and (b) 1·(AgNO3)2 with thermal ellipsoids at 50% probability. Counteranions are omitted for clarity in the side view of complex 2(OCMe2). C: gray, N: blue, Ag: orange, O: red, S: deep blue, and F: green.
Figure 5
Figure 5
Synthesis of binuclear gold complex 3.
Figure 6
Figure 6
(a) Solid-state structure of complex 3 with thermal ellipsoids at 50% probability. Hydrogen atoms and counteranions are omitted for clarity. C: gray, N: blue, and Au: yellow. (b) Intermolecular aurophilic interaction in 3.
Figure 7
Figure 7
Synthesis of binuclear copper complex 4.
Figure 8
Figure 8
Solid-state structure of complex 4 with thermal ellipsoids at 50% probability. Hydrogen atoms and counteranions are omitted for clarity. C: gray, N: blue, and Cu: orange.
Figure 9
Figure 9
DFT calculations of the proximal binuclear copper, silver, and gold complexes.
See this image and copyright information in PMC

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