Formation of a Dinuclear Mercury(II) Complex with a Regular Bis‐Strapped Porphyrin Following a Tunable Cooperative Process

Motreff, Nicolas; Gac, Stéphane Le; Luhmer, Michel; Furet, Éric; Halet, Jean‐François; Roisnel, Thierry; Boitrel, Bernard

doi:10.1002/ange.201007007

Cited by 10 publications

(7 citation statements)

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“…www.chemeurj.org no intermediate monometallic species were observed during the metallation process. [10] An analytical sample of 1Cd 2 was prepared and isolated upon precipitation in a methanol/ water mixture, and its elemental analysis confirmed the bimetallic nature of the complex. Single crystals were grown from slow evaporation of the NMR tube solution of the titration experiment and were subjected to X-ray diffraction analysis.…”

Section: Resultsmentioning

confidence: 93%

“…[18] Such bimetallic complexes involving a regular porphyrin as a bridging ligand have been scarcely reported. [9,10,19] Figure 2 b shows a comparison of the coordination spheres of 1Cd 2 with those of the related lead(II) and mercury(II) bime-…”

Section: Resultsmentioning

confidence: 99%

“…and 1Hg 2 [10] (selected distances in Table 1). In the cases of lead(II) and mercury(II), the environment of each metal atom is characterized by a short metal-nitrogen distance (Pb1 À N4 and Pb2 À N2; Hg1 À -N2 and Hg2 À N4), as well as a long one with the opposite nitrogen atom of the N core (Pb1ÀN2 and Pb2ÀN4; Hg1ÀN4 and Hg2À N2).…”

Section: Resultsmentioning

confidence: 99%

“…b) Ball-and-stick views of the coordination sphere of the lead, cadmium and mercury atoms in the crystal structures of 1Pb 2 , [9a] 1Cd 2 , and 1Hg 2 . [10] For 1Pb 2 and 1Hg 2 , Os1-Os4 are oxygen atoms of DMSO molecules.…”

Section: Resultsmentioning

confidence: 99%

“…The system involves a bis-strapped porphyrin ligand functionalized with an overhanging carboxylic acid group on each side of the macrocycle (1, Scheme 2). [8] This homoditopic ligand can generate two types of homobimetallic complexes with Pb II and Bi III ions: [9] 1) C 2 -symmetric complexes with both metal ions in-teracting with the N core and a COO À group of a strap, with the porphyrin acting as a bridging ligand (1A C H T U N G T R E N N U N G (BiOAc) 2 and 1Pb 2 , Scheme 2); [10] and 2) dissymmetric complexes in which one cation is bound to the N core (out-of-plane coordination mode, OOP) whereas the other one interacts exclusively with the strap on the opposite side (hanging-atop coordination mode, HAT;…”

Section: Introductionmentioning

confidence: 99%

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Formation and Dynamic Behavior of Mono‐ and Bimetallic Cadmium(II) Porphyrin Complexes: Allosteric Control of Coupled Intraligand Metal Migrations

Gac

Fusaro

Dorcet

et al. 2013

Chemistry A European J

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The complexation behavior of a bis-strapped porphyrin ligand (1) towards Cd(II) has been investigated by (1)H and (113)Cd NMR spectroscopy with the help of X-ray diffraction structures. The presence of an overhanging carboxylic acid group on each side of the macrocycle is responsible for the instantaneous insertion of the metal ion(s) at room temperature, and allows the formation of bimetallic species with unusual coordination modes at the origin of unique dynamic behaviors. In the absence of base, a C2-symmetric bimetallic complex (1Cd2 ) is readily formed, in which the porphyrin acts as a bridging ligand. Both Cd(II) ions are bound to the N core and to a COO(-) group of a strap. In contrast, the presence of a base induces a two-step binding process with the successive formation of mono and bimetallic species (1(Cd) and 1(Cd)·CdOAc). Formally, a Cd(II) ion is first inserted into the N core and experiences a strong out-of-plane (OOP) displacement due to the binding of an overhanging carbonyl group in an apical position. A second Cd(II) ion then binds exclusively to the strap on the opposite side, in a so-called hanging-atop (HAT) coordination mode. These two complexes display a fluxional behavior that relies on intraligand migration processes of the metal ion(s). In 1(Cd), the Cd(II) ion exchanges between the two equivalent overhanging apical ligands by funneling through the porphyrin ring. In 1(Cd)·CdOAc, the two Cd(II) ions exchange their coordination mode (HAT↔OOP) in a concerted way while staying on their respective side of the macrocycle, in a so-called Newton's cradle-like motion. The intramolecular pathway was notably evidenced by variable temperature (113) Cd heteronuclear NMR experiments. This coupled motion of the Cd(II) cations is under allosteric control; the addition of an acetate anion (the allosteric effector) to the "resting" C2-symmetric complex 1Cd2 affords the dissymmetric complex 1(Cd)·CdOAc and triggers equilibrium between its two degenerate states. The rate of the swinging motion further depends on the concentration of AcO(-), with a higher concentration leading to a slower motion. As compared with the related Pb(II) and Bi(III) bimetallic complexes, the Newton's cradle-like motion proceeds faster with the smaller Cd(II) ion. These results open the way to novel multistable devices and switches.

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Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Formation and Dynamic Behavior of Mono‐ and Bimetallic Cadmium(II) Porphyrin Complexes: Allosteric Control of Coupled Intraligand Metal Migrations

Gac

Fusaro

Dorcet

et al. 2013

Chemistry A European J

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Sunlight‐Driven Formation and Dissociation of a Dynamic Mixed‐Valence Thallium(III)/Thallium(I) Porphyrin Complex

et al. 2015

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Inspired by a Newtons cradle device and interested in the development of redox-controllable bimetallic molecular switches, a mixed-valence thallium(III)/thallium(I) bis-strap porphyrin complex, with Tl III bound out of the plane of the N core and Tl I hung to a strap on the opposite side, was formed by the addition of TlOAc to the free base and exposure to indirect sunlight. In this process, oxygen photosensitization by the porphyrin allows the oxidation of Tl I to Tl III . The bimetallic complex is dynamic as the metals exchange their positions symmetrically to the porphyrin plane with Tl III funneling through the macrocycle. Further exposure of the complex to direct sunlight leads to thallium dissociation and to total recovery of the free base. Hence, the porphyrin plays a key role at all stages of the cycle of the complex: It hosts two metal ions, and by absorbing light, it allows the formation and dissociation of Tl III . These results constitute the basis for the further design of innovative light-driven bimetallic molecular devices.[*] V.

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β,β′‐Bipyrrole Fusion‐Driven cis‐Bimetallic Complexation in Isomeric Porphyrin

2015

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An unprecedented cis‐bimetallic complex of dinaphthoporphycene (DNP), namely [Pd2(μ‐DNP)(μ‐OAc)2], is reported. The most striking feature of this complex is that two palladiums coordinate to the macrocycle on the same side and are closely held together (PdPd: 2.67 Å) by two bridging acetate ligands exhibiting significant metal–metal bonding interaction (bond order 0.18 evaluated by NBO analysis). Interestingly, replacing acetate with acetylacetonate (acac) could stabilize an unusual mono‐palladium complex of DNP, where Pd coordinates unsymmetrically to two ring Ns above the macrocyclic plane, as well as coordinating with two Os of the acac ligand. Remarkably, the rigid DNP core displays enhanced complexation induced aromaticity (as per NICS and HOMA analysis), despite undergoing severe core deformation during complexation with metal ion(s) as noticed from their solid‐state structures.

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Formation of a Dinuclear Mercury(II) Complex with a Regular Bis‐Strapped Porphyrin Following a Tunable Cooperative Process

Cited by 10 publications

References 20 publications

Formation and Dynamic Behavior of Mono‐ and Bimetallic Cadmium(II) Porphyrin Complexes: Allosteric Control of Coupled Intraligand Metal Migrations

Formation and Dynamic Behavior of Mono‐ and Bimetallic Cadmium(II) Porphyrin Complexes: Allosteric Control of Coupled Intraligand Metal Migrations

Sunlight‐Driven Formation and Dissociation of a Dynamic Mixed‐Valence Thallium(III)/Thallium(I) Porphyrin Complex

β,β′‐Bipyrrole Fusion‐Driven cis‐Bimetallic Complexation in Isomeric Porphyrin

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