Chimie de coordination avec les ligands organiques de type salicyl - - PowerPoint PPT Presentation

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Chimie de coordination avec les ligands organiques de type salicyl - - PowerPoint PPT Presentation

May 25, 2023 387 likes •833 views

DECOMET laboratory- UMR-CNRS 7177 Magic ligand There is something in the air ! Air Fe +II Fe +III H 2 0 Chimie de coordination avec les ligands organiques de type salicyl hydrazine : quand les bonnes surprises se succdent ! Research

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DECOMET laboratory- UMR-CNRS 7177

Air H20 Fe+II Fe+III

There is something in the air !

Magic ligand

Chimie de coordination avec les ligands organiques de type salicyl hydrazine : quand les bonnes surprises se succèdent !

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Research topics in 2000

Intermetallic compounds (CaMn2Ge2)

TN = 675 K

R.Welter, J.MMM., 1998, 187, 278

Single Molecule Magnet [Mn12(CH3COO)16(H2O)4O12]

TB = 5 K

  • T. Lis, Acta Cryst., 1980, B36, 2042
  • D. Gatteschi et al, Nature, 1993, 365

Coordination chemistry <-> molecular magnetism

New magnetic materials - New magnetic systems ?

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Methodology

1) Ligands design. 1) Ligands design. 1) Ligands design. 2) Mononuclear complexes 4) Binuclear complexes 3) Crystal and magnetic parameters determination 5) Full magneto-crystal chemistry.

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2-hydroxy-1,3-dithiolan-2-ylidenehydrazide benzoïque acid (H2L_2)

Asymmetric unit of H2L_2 Supramolecular packing of H2L_2 along the a axis Orthorhombic space group : P n a 21 Formula : C10H10N2O2S2

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2-hydroxy[bis(methylthio)methylene]hydrazide benzoique acide (H2L_3)

Asymmetric unit of H2L_3 supramolecular packing of H2L_3 along the b axis

They run together !

Orthorhombic space group : P b c a Formula : C10H12N2O2S2

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They run again ! ---> ligands ready for the competition?

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8

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Synthesis and Magnetic Properties of New Mono- and Binuclear Iron Complexes with Salicyloylhydrazono Dithiolane Ligand, Bouslimani, N.; Clément, N.; Rogez, G.; Turek, P.; Bernard, M.; Dagorne, S.; Martel, D.; Cong, H. N.; Welter, R.

  • Inorg. Chem.; (Article); 2008; 47(17); 7623-7630.

Iron complexes

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A photo reduction process

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Fe+III complex --- Ligand -1 (basic form)

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Fe+II complex --- Ligand O (acid form)

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Synthesis and Magnetic Properties of New Mono- and Binuclear Iron Complexes with Salicyloylhydrazono Dithiolane Ligand Bouslimani, N.; Clément, N.; Rogez, G.; Turek, P.; Bernard, M.; Dagorne, S.; Martel, D.; Cong, H. N.; Welter, R.

  • Inorg. Chem.; (Article); 2008; 47(17); 7623-7630.
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[Fe+2]

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[Fe+3]

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Light Induced Reduction of Iron (III) to Iron (II)

Only one exemple founded in 1955 - EDTA/not well characterized

Large application in electricity production and storage at low cost :

Patent (2009)

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Proposed mecanism

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Easy access to iron on earth

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Photo device given 310 mV et 15 μA.

Easy technology Low cost ‘green’

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!

Power vs I : a classical cell

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  • Energy storage
  • Chemical reduction process : Cu2+ -->

Cu+1 for instance

  • Nanoelectronics : molecular switch

induced by light ✴ Depollution (CrVI -> CrIII) ✴ etc... Other applications

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N H N O OH S S N H N O N H N O S S N H N O OH

H2L2 H2L7 HL5 HL6

Other candidates

Spontaneous Reduction of High-Spin FeIII Complexes Supported by Benzoic Hydrazide Derivative Ligands.

  • N. Bouslimani, N. Clément , C. Toussaint, S. Hameury, P. Turek, S.

Choua, S. Dagorne, D. Martelc and R. Welter European Journal of Inorganic Chemistry, (2009), 3734-3741

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2010 --> I. S. 2, private compagny

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Another application of photo reduction

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+ 2 FeCl3 4HCl +

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Fe(DMF)62++ FeCl42- H4L

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DARK LIGHT

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Molecular magnetism

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Iron(III) dimer

Synthesis and Magnetic Properties of New Mono- and Binuclear Iron Complexes with Salicyloylhydrazono Dithiolane Ligand, Bouslimani, N.; Clément, N.; Rogez, G.; Turek, P.; Bernard, M.; Dagorne, S.; Martel, D.; Cong, H. N.; Welter, R.

  • Inorg. Chem.; (Article); 2008; 47(17); 7623-7630.

2004 : starting point : paramagnetic dimers

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Fe(III)2(µ-OMe)2(HL_2)4 complex (Electronic configuration)

Antiferro : -30 cm-1

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  • R. Welter et al., J. AM. CHEM. SOC. 2006, 128, 3140-3141

Strongest ferromagnetic interaction to date for MnIII-MnIII dimers !

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Mn(III)2(µ-OMe)2(HL_2)4 complex (DFT calculations)

J = +18,2 cm-1

(D = -0.35 cm-1, E/|D| = 0.19)

Magnetic orbitals in Mn(III)2(µ-OMe)2(HL(2))4 alpha HOMO (blue) and HOMO-1 (red)

  • R. Welter et al., J. AM. CHEM. SOC. 2006, 128, 3140-3141
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Mn(III)2(µ-OMe)2(HL_2)4 complex (Electronic configuration)

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? ?

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Symmetric = AF Asymmetric = Ferro ?

First example Same structure as Mn2 with strong ferro coupling

Novel Cr-III dinuclear complexes supported by salicyloylhydrazono dithiolane and dithiane ligands: Synthesis, stability, crystal structures and magnetic properties Clement Nicolas, Toussaint Clement, Rogez Guillaume, Loose Claudia, Kortus Jens, Brelot Lydia, Choua Sylvie, Dagorne Samuel, Turek Philippe, Welter Richard. Dalton Trans. (2010) 39, 19, 4579-4585

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Acknowledgments Laboratoire ‘Densité Electronique et COordination METallique’

DECOMET ( UMR CNRS-7177 )

B.Malaman - I. Ijaali - V.Klosek - G.Venturini - A.Vernière - N.Hansen✞,

  • K. Halich, P. Braunstein, N. Bouslimani, A et C Beghidja, N. Clément,
  • K. Cheaib, D. Specklin, C. Toussaint, M. Guth, D. Welsch, D. Martel,..
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