Heterobimetallic Porphyrin Complexes Displaying Triple Dynamics: Coupled Metal Motions Controlled by Constitutional Evolution.

Stephane Le Gac, Luca Fusaro, Thierry Roisnel, Bernard. Boitrel

Research output: Contribution to journalArticle

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Abstract

A bis-strap porphyrin ligand (1), with an overhanging carboxylic acid group on each side of the macrocycle, has been investigated toward the formation of dynamic libraries of bimetallic complexes with Hg(II), Cd(II), and Pb(II). Highly heteroselective metalation processes occurred in the presence of Pb(II), with Hg(II) or Cd(II) bound out-of-plane to the N-core and "PbOAc" bound to a carboxylate group of a strap on the opposite side. The resulting complexes, 1-Hg·PbOAc and 1-Cd·PbOAc, display three levels of dynamics. The first is strap-level (interactional dynamics), where the PbOAc moiety swings between the left and right side of the strap owing to a second sphere of coordination with lateral amide functions. The second is ligand-level (motional dynamics), where 1-Hg·PbOAc and 1-Cd·PbOAc exist as two degenerate states in equil. controlled by a chem. effector (AcO-). The process corresponds to a double translocation of the metal ions according to an intramol. migration of Hg(II) or Cd(II) through the N-core, oscillating between the two equiv. overhanging carbonyl groups, coupled to an intermol. pathway for PbOAc exchanging between the two equiv. overhanging carboxylate groups (N-coreup ↹ N-coredown coupled to strapdown ↹ strapup, i.e., coupled motion #1 in the abstr. graphic). The third is library-level (constitutional dynamics), where a dynamic constitutional evolution of the system was achieved by the successive addn. of two chem. effectors (DMAP and then AcO-). It allowed shifting equil. forward and backward between 1-Hg·PbOAc and the corresponding homobimetallic complexes 1Hg2·DMAP and 1-Pb·PbOAc. The latter displays a different ligand-level dynamics, as an intraligand coupled migration of the Pb(II) ions (N-coreup ↹ strapup coupled to strapdown ↹ N-coredown, i.e., coupled motion #2 in the abstr. graphic). In addn., the neutral "bridged" complexes 1HgPb and 1CdPb, with the metal ions on opposite sides both bound to the N-core and to a carboxylate of a strap, were structurally characterized. These results establish an unprecedented approach in supramol. coordination chem., by considering the reversible interaction of a metal ion with the porphyrin N-core as a new source of self-organization processes. This work should provide new inspirations for the design of innovative adaptative materials and devices. [on SciFinder(R)]
Original languageEnglish
Pages (from-to)6698-6715
Number of pages18
JournalJournal of the American Chemical Society
Volume136
Issue number18
DOIs
Publication statusPublished - 2014
Externally publishedYes

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Porphyrins
Metals
Ions
Ligands
Libraries
Metal ions
Carboxylic Acids
Amides
Equipment and Supplies
Carboxylic acids
Display devices

Keywords

  • metal exchange fluxional dynamics heterobimetallic strap porphyrin complex
  • prepn heterobimetallic strap porphyrin complex

Cite this

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title = "Heterobimetallic Porphyrin Complexes Displaying Triple Dynamics: Coupled Metal Motions Controlled by Constitutional Evolution.",
abstract = "A bis-strap porphyrin ligand (1), with an overhanging carboxylic acid group on each side of the macrocycle, has been investigated toward the formation of dynamic libraries of bimetallic complexes with Hg(II), Cd(II), and Pb(II). Highly heteroselective metalation processes occurred in the presence of Pb(II), with Hg(II) or Cd(II) bound out-of-plane to the N-core and {"}PbOAc{"} bound to a carboxylate group of a strap on the opposite side. The resulting complexes, 1-Hg·PbOAc and 1-Cd·PbOAc, display three levels of dynamics. The first is strap-level (interactional dynamics), where the PbOAc moiety swings between the left and right side of the strap owing to a second sphere of coordination with lateral amide functions. The second is ligand-level (motional dynamics), where 1-Hg·PbOAc and 1-Cd·PbOAc exist as two degenerate states in equil. controlled by a chem. effector (AcO-). The process corresponds to a double translocation of the metal ions according to an intramol. migration of Hg(II) or Cd(II) through the N-core, oscillating between the two equiv. overhanging carbonyl groups, coupled to an intermol. pathway for PbOAc exchanging between the two equiv. overhanging carboxylate groups (N-coreup ↹ N-coredown coupled to strapdown ↹ strapup, i.e., coupled motion #1 in the abstr. graphic). The third is library-level (constitutional dynamics), where a dynamic constitutional evolution of the system was achieved by the successive addn. of two chem. effectors (DMAP and then AcO-). It allowed shifting equil. forward and backward between 1-Hg·PbOAc and the corresponding homobimetallic complexes 1Hg2·DMAP and 1-Pb·PbOAc. The latter displays a different ligand-level dynamics, as an intraligand coupled migration of the Pb(II) ions (N-coreup ↹ strapup coupled to strapdown ↹ N-coredown, i.e., coupled motion #2 in the abstr. graphic). In addn., the neutral {"}bridged{"} complexes 1HgPb and 1CdPb, with the metal ions on opposite sides both bound to the N-core and to a carboxylate of a strap, were structurally characterized. These results establish an unprecedented approach in supramol. coordination chem., by considering the reversible interaction of a metal ion with the porphyrin N-core as a new source of self-organization processes. This work should provide new inspirations for the design of innovative adaptative materials and devices. [on SciFinder(R)]",
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author = "{Le Gac}, Stephane and Luca Fusaro and Thierry Roisnel and Bernard. Boitrel",
note = "M1 - Copyright (C) 2014 American Chemical Society (ACS). All Rights Reserved. CAPLUS AN 2014:651430(Journal; Online Computer File)",
year = "2014",
doi = "10.1021/ja501926f",
language = "English",
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Heterobimetallic Porphyrin Complexes Displaying Triple Dynamics: Coupled Metal Motions Controlled by Constitutional Evolution. / Le Gac, Stephane; Fusaro, Luca; Roisnel, Thierry; Boitrel, Bernard.

In: Journal of the American Chemical Society, Vol. 136, No. 18, 2014, p. 6698-6715.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Heterobimetallic Porphyrin Complexes Displaying Triple Dynamics: Coupled Metal Motions Controlled by Constitutional Evolution.

AU - Le Gac, Stephane

AU - Fusaro, Luca

AU - Roisnel, Thierry

AU - Boitrel, Bernard.

N1 - M1 - Copyright (C) 2014 American Chemical Society (ACS). All Rights Reserved. CAPLUS AN 2014:651430(Journal; Online Computer File)

PY - 2014

Y1 - 2014

N2 - A bis-strap porphyrin ligand (1), with an overhanging carboxylic acid group on each side of the macrocycle, has been investigated toward the formation of dynamic libraries of bimetallic complexes with Hg(II), Cd(II), and Pb(II). Highly heteroselective metalation processes occurred in the presence of Pb(II), with Hg(II) or Cd(II) bound out-of-plane to the N-core and "PbOAc" bound to a carboxylate group of a strap on the opposite side. The resulting complexes, 1-Hg·PbOAc and 1-Cd·PbOAc, display three levels of dynamics. The first is strap-level (interactional dynamics), where the PbOAc moiety swings between the left and right side of the strap owing to a second sphere of coordination with lateral amide functions. The second is ligand-level (motional dynamics), where 1-Hg·PbOAc and 1-Cd·PbOAc exist as two degenerate states in equil. controlled by a chem. effector (AcO-). The process corresponds to a double translocation of the metal ions according to an intramol. migration of Hg(II) or Cd(II) through the N-core, oscillating between the two equiv. overhanging carbonyl groups, coupled to an intermol. pathway for PbOAc exchanging between the two equiv. overhanging carboxylate groups (N-coreup ↹ N-coredown coupled to strapdown ↹ strapup, i.e., coupled motion #1 in the abstr. graphic). The third is library-level (constitutional dynamics), where a dynamic constitutional evolution of the system was achieved by the successive addn. of two chem. effectors (DMAP and then AcO-). It allowed shifting equil. forward and backward between 1-Hg·PbOAc and the corresponding homobimetallic complexes 1Hg2·DMAP and 1-Pb·PbOAc. The latter displays a different ligand-level dynamics, as an intraligand coupled migration of the Pb(II) ions (N-coreup ↹ strapup coupled to strapdown ↹ N-coredown, i.e., coupled motion #2 in the abstr. graphic). In addn., the neutral "bridged" complexes 1HgPb and 1CdPb, with the metal ions on opposite sides both bound to the N-core and to a carboxylate of a strap, were structurally characterized. These results establish an unprecedented approach in supramol. coordination chem., by considering the reversible interaction of a metal ion with the porphyrin N-core as a new source of self-organization processes. This work should provide new inspirations for the design of innovative adaptative materials and devices. [on SciFinder(R)]

AB - A bis-strap porphyrin ligand (1), with an overhanging carboxylic acid group on each side of the macrocycle, has been investigated toward the formation of dynamic libraries of bimetallic complexes with Hg(II), Cd(II), and Pb(II). Highly heteroselective metalation processes occurred in the presence of Pb(II), with Hg(II) or Cd(II) bound out-of-plane to the N-core and "PbOAc" bound to a carboxylate group of a strap on the opposite side. The resulting complexes, 1-Hg·PbOAc and 1-Cd·PbOAc, display three levels of dynamics. The first is strap-level (interactional dynamics), where the PbOAc moiety swings between the left and right side of the strap owing to a second sphere of coordination with lateral amide functions. The second is ligand-level (motional dynamics), where 1-Hg·PbOAc and 1-Cd·PbOAc exist as two degenerate states in equil. controlled by a chem. effector (AcO-). The process corresponds to a double translocation of the metal ions according to an intramol. migration of Hg(II) or Cd(II) through the N-core, oscillating between the two equiv. overhanging carbonyl groups, coupled to an intermol. pathway for PbOAc exchanging between the two equiv. overhanging carboxylate groups (N-coreup ↹ N-coredown coupled to strapdown ↹ strapup, i.e., coupled motion #1 in the abstr. graphic). The third is library-level (constitutional dynamics), where a dynamic constitutional evolution of the system was achieved by the successive addn. of two chem. effectors (DMAP and then AcO-). It allowed shifting equil. forward and backward between 1-Hg·PbOAc and the corresponding homobimetallic complexes 1Hg2·DMAP and 1-Pb·PbOAc. The latter displays a different ligand-level dynamics, as an intraligand coupled migration of the Pb(II) ions (N-coreup ↹ strapup coupled to strapdown ↹ N-coredown, i.e., coupled motion #2 in the abstr. graphic). In addn., the neutral "bridged" complexes 1HgPb and 1CdPb, with the metal ions on opposite sides both bound to the N-core and to a carboxylate of a strap, were structurally characterized. These results establish an unprecedented approach in supramol. coordination chem., by considering the reversible interaction of a metal ion with the porphyrin N-core as a new source of self-organization processes. This work should provide new inspirations for the design of innovative adaptative materials and devices. [on SciFinder(R)]

KW - metal exchange fluxional dynamics heterobimetallic strap porphyrin complex

KW - prepn heterobimetallic strap porphyrin complex

U2 - 10.1021/ja501926f

DO - 10.1021/ja501926f

M3 - Article

VL - 136

SP - 6698

EP - 6715

JO - J. Am. Chem. Soc.

JF - J. Am. Chem. Soc.

SN - 0002-7863

IS - 18

ER -