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Bossek U, Nühlen D, Bill E, et al. Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LM(II)(&mgr;-X)(3)M(II)L]BPh(4) (M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane). Inorg Chem. 1997;36(13):2834-2843doi: 10.1021/ic970119h.
Bossek, U., Nühlen, D., Bill, E., Glaser, T., Krebs, C., Weyhermüller, T., Wieghardt, K., Lengen, M., & Trautwein, A. X. (1997). Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LM(II)(&mgr;-X)(3)M(II)L]BPh(4) (M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane). Inorganic chemistry, 36(13), 2834-2843. https://doi.org/10.1021/ic970119h
Bossek, Ursula, et al. "Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LM(II)(&mgr;-X)(3)M(II)L]BPh(4) (M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane)." Inorganic chemistry vol. 36,13 (1997): 2834-2843. doi: https://doi.org/10.1021/ic970119h
Bossek U, Nühlen D, Bill E, Glaser T, Krebs C, Weyhermüller T, Wieghardt K, Lengen M, Trautwein AX. Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LM(II)(&mgr;-X)(3)M(II)L]BPh(4) (M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane). Inorg Chem. 1997 Jun 18;36(13):2834-2843. doi: 10.1021/ic970119h. PMID: 11669919.
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Inorg Chem. 1997 Jun 18;36(13):2834-2843. doi: 10.1021/ic970119h.

Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LM(II)(&mgr;-X)(3)M(II)L]BPh(4) (M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane).

Inorganic chemistry

Ursula Bossek, Daniela Nühlen, Eckhard Bill, Thorsten Glaser, Carsten Krebs, Thomas Weyhermüller, Karl Wieghardt, Marek Lengen, A. X. Trautwein

Affiliations

  1. Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany, and Institut für Physik, Medizinische Universität, D-23538 Lübeck, Germany.

PMID: 11669919 DOI: 10.1021/ic970119h

Abstract

The reaction of the divalent metal halides ZnCl(2), ZnBr(2), MnCl(2).4CH(3)CN, MnBr(2), FeCl(2).4CH(3)CN, CoCl(2).4CH(3)CN, CoBr(2), NiCl(2).6H(2)O, and NiBr(2), respectively, with the macrocycle 1,4,7-trimethyl-1,4,7-triazacyclononane (L) (1:1) in anhydrous acetonitrile, acetone, chloroform, or ethanol affords upon additon of NaBPh(4) the isomorphous series of complexes [LM(II)(&mgr;-X)(3)M(II)L]BPh(4): 1, M = Zn, X = Cl; 2, Zn, Br; 3, Mn, Cl; 4, Mn, Br; 5, Fe, Cl; 6, Co, Cl; 7, Co, Br; 8, Ni, Cl; 9, Ni, Br. Six of these complexes have been structurally characterized by single-crystal X-ray crystallography; they crystallize in the triclinic space group P&onemacr; (No. 2) with Z = 4. Crystal data are as follows 1, a = 16.654(1), b = 17.042(1), c = 17.684(1) Å, alpha = 97.30(1), beta = 93.58(1), gamma = 117.46(1) degrees; 3, a = 16.632(8), b = 17.012(8), c = 17.855(5) Å, alpha = 97.16(3), beta = 93.37(3), gamma = 117.24(3) degrees; 5, a = 16.658(3), b = 17.064(3), c = 17.741(4) Å, alpha = 97.32(3), beta = 93.47(3), gamma = 117.36(3) degrees; 6, a = 16.640(3), b = 17.040(3), c = 17.686(4) Å, alpha = 97.39(3), beta = 93.58(3), gamma = 117.39(3) degrees; 8, a = 16.608(3), b = 16.995(3), c = 17.555(3) Å, alpha = 97.36(1), beta = 93.52(1), gamma = 117.52(1) degrees; 9, a = 16.680(3), b = 17.016(2), c = 17.715(3)Å, alpha = 96.99(1), beta = 93.70(1), gamma = 117.42(1) degrees. All complexes consist of a dinuclear, face-sharing bioctahedral monocation with three &mgr;(2)-Cl or &mgr;(2)-Br bridging ligands and two LM fragments and well-separated tetraphenylborate anions (1:1). The cations cocrystallize in two different forms: an enantiomeric form with (lambdalambdalambda) (or (deltadeltadelta)) conformation at both LM fragments and a meso form with an (lambdalambdalambda) conformation at one LM fragment and (deltadeltadelta) at the other (ratio 1:1). From temperature-dependent magnetic susceptibility measurements (2-293 K) it was established that the spins of the unpaired electrons in 3 (d(5)d(5) high spin), 4 (d(5)d(5)), 6 (d(7)d(7) high spin), 7 (d(7)d(7)), 8 (d(8)d(8)), and 9 (d(8)d(8)) are intramolecularly, weakly antiferromagnetically coupled in each case. Surprisingly, the spins order ferromagnetically in 5 (d(6)d(6) high spin). This is in contrast to the previously reported complex [(thf)(3)Fe(II)(&mgr;-Cl)(3)Fe(II)(thf)(3)][SnCl(5)(thf)] (thf = tetrahydrofuran)(5) for which a new analysis of the temperature-dependence of the magnetic susceptibility and of field-dependent Mössbauer spectra establish a weak intramolecular antiferromagnetic coupling. The origin of this difference is analyzed.

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