title: Realization of unusual ligand binding motifs in metalated container molecules: synthesis, structures, and magnetic properties of the complexes [(LMe)Ni2(mu-L')]n+ with L'=NO3-, NO2-, N3-, N2H4, pyridazine, phthalazine, pyrazolate, and benzoate.
abstract: A series of dinickel(II) complexes with the 24-membered macrocyclic hexaazadithiophenol ligand H(2)L(Me) was prepared and examined. The doubly deprotonated form (L(Me))(2-) forms complexes of the type [(L(Me))Ni2II(mu-L')](n+) with a bioctahedral N(3)Ni(II)(mu-SR)(2)(mu-L')Ni(II)N(3) core and an overall calixarene-like structure. The bridging coordination site L' is accessible for a wide range of exogenous coligands. In this study L'=NO(3)(-), NO(2)(-), N(3)(-), N(2)H(4), pyrazolate (pz), pyridazine (pydz), phthalazine (phtz), and benzoate (OBz). Crystallographic studies reveal that each substrate binds in a distinct fashion to the [(L(Me))Ni(2)](2+) portion: NO(2)(-), N(2)H(4), pz, pydz, and phtz form mu(1,2)-bridges, whereas NO(3)(-), N(3)(-), and OBz(-) are mu(1,3)-bridging. These distinctive binding motifs and the fact that some of the coligands adopt unusual conformations is discussed in terms of complementary host-guest interactions and the size and form of the binding pocket of the [(L(Me))Ni(2)](2+) fragment. UV/Vis and electrochemical studies reveal that the solid-state structures are retained in the solution state. The relative stabilities of the complexes indicate that the [(L(Me))Ni(2)](2+) fragment binds anionic coligands preferentially over neutral ones and strong-field ligands over weak-field ligands. Secondary van der Waals interactions also contribute to the stability of the complexes. Intramolecular ferromagnetic exchange interactions are present in the nitrito-, pyridazine-, and the benzoato-bridged complexes where J=+6.7, +3.5, and +5.8 cm(-1) (H=-2 JS(1)S(2), S(1)=S(2)=1) as indicated by magnetic susceptibility data taken from 300 to 2 K. In contrast, the azido bridge in [(L(Me))Ni(2)(mu(1,3)-N(3))](+) results in an antiferromagnetic exchange interaction J=-46.7 cm(-1). An explanation for this difference is qualitatively discussed in terms of bonding differences.
authors.affiliation: Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstrasse 21, 79104 Freiburg, Germany.
authors.forename: Julia
authors.initials: J
authors.lastname: Hausmann
authors.forename: Marco H
authors.initials: MH
authors.lastname: Klingele
authors.forename: Vasile
authors.initials: V
authors.lastname: Lozan
authors.forename: Gunther
authors.initials: G
authors.lastname: Steinfeld
authors.forename: Dieter
authors.initials: D
authors.lastname: Siebert
authors.forename: Yves
authors.initials: Y
authors.lastname: Journaux
authors.forename: Jean Jacques
authors.initials: JJ
authors.lastname: Girerd
authors.forename: Berthold
authors.initials: B
authors.lastname: Kersting
mesh_terms: D001386:Azides / Q000737:chemistry; D001565:Benzoates / Q000737:chemistry*; D001665:Binding Sites; D003035:Cobalt / Q000737:chemistry; D008024:Ligands; D008280:Magnetics; D008956:Models, Chemical; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D009566:Nitrates / Q000737:chemistry; D009569:Nitric Oxide / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010793:Phthalazines / Q000737:chemistry*; D011720:Pyrazoles / Q000737:chemistry*; D011724:Pyridazines / Q000737:chemistry*
chemical_list: D001386:Azides; D001565:Benzoates; D008024:Ligands; D009566:Nitrates; D009942:Organometallic Compounds; D010793:Phthalazines; D011720:Pyrazoles; D011724:Pyridazines; D009569:Nitric Oxide; D003035:Cobalt; C062482:pyridazine; D009532:Nickel; C043388:phthalazine