Long-range magnetic coupling through extended π-conjugated aromatic bridges in dinuclear copper(II) metallacyclophanes

Journal of the American Chemical Society

Volumn 125, Issue 36, 2003, Pages 10770-10771

  Pardo, Emilio ^a   Faus, Juan ^a   Julve, Miguel ^a   Lloret, Francesc ^a   Muñoz, M Carmen ^b   Cano, Joan ^c   Ottenwaelder, Xavier ^c   Journaux, Yves ^c   Carrasco, Rosa ^d   Blay, Gonzalo ^a   Fernández, Isabel ^a   Ruiz García, Rafael ^a  

^a UNIVERSITY OF VALENCIA   (Spain)

^b UNIVERSITAT POLITÈCNICA DE VALÈNCIA   (Spain)

^c UNIVERSITÉ PARIS SACLAY   (France)

^d UNIVERSITÉ PARIS SUD   (France)

Author keywords

[No Author keywords available]

Indexed keywords

COPPER COMPLEX; COPPER METALLOCYCLOPHANE; CYCLOPHANE DERIVATIVE; N,N' 1,4 PHENYLENEBIS(OXAMATE); N,N' 4,4' BIPHENYLENEBIS(OXAMATE); OXAMIC ACID; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BOND; CHEMICAL STRUCTURE; CONJUGATION; ELECTRON TRANSPORT; MAGNETISM; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0043236238     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja030060f     Document Type: Article

References (11)

1. Kahn, O. Molecular Magnetism; VCH Publishers: New York. 1993.
2. (a) Hay, J. P.; Thibeault, J. C.; Hoffmann, R. J. Am. Chem. Soc. 1975, 97, 4884.
3. (b) Coffman, R. E.; Buettner, G. R. J. Phys Chem. 1979, 83, 2387.
4. (c) Kahn, O. Angew. Chem., Int. Ed. Engl. 1985, 24, 834.
5. Felthouse, T. R.; Duesler, E. N.; Hendrickson, D. N. J. Am. Chem. Soc. 1978, 100, 618.
6. Kolks, G.; Lippard, S. J.; Waszcak, J. V.; Lilienthal, H. R. J. Am. Chem. Soc. 1982, 104, 717.
7. Chaudhuri, P.; Oder, K.; Wieghardt, K.; Gehring, S.; Haase, W.; Nuber, B.; Weiss, J. J. Am. Chem. Soc. 1988, 110, 3657.
8. Fernández, I.; Ruiz, R.; Faus, J.; Julve, M.; Lloret, F.; Cano, J.; Ottenwaelder, X.; Journaux, Y.; Muñoz, M. C. Angew. Chem., Int. Ed. 2001, 40, 3039.
9. -1 respectively) (Table S1). In light of our results, it appears that the exchange interaction in these compounds also involves predominantly π-orbital pathways.
10. Molecular geometries for 1-5 were not optimized, but their structural dimensions were taken from the crystal structure of 1B (ø = 90°). For 2-5, the phenylene rings connected by the C-C single bond were coplanar (ψ = 0°) and the C-C inter-ring distance was taken as 1.49 Å.
11. Preliminary DFT energy calculations show that the calculated singlet-triplet energy gap is sensitive to the dihedral angle between the copper and phenylene planes (ø) in 1 and that between the phenylene planes (ψ) in 2. Thus, the -J value becomes smaller as the more different from 90° is ø and from 0° is ψ, as a result of these global torsions around the C-N and C-C single bonds of the aromatic diamide bridges (data reported elsewhere).