Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni II 2 (L)(µ 1,1 -N 3 )][ClO 4 ] (L = Macrocyclic N 6 S 2 Ligand)

Abstract

The dinuclear NiII complex [Ni2(L2 )][ClO4]2 (3) supported by the 28-membered hexaazadithiophenolate macrocycle (L2 ) 2 binds the N3  ion specifically end-on yielding [Ni2(L2 )(1,1- N3)][ClO4] (7) or [Ni2(L2 )(1,1-N3)][BPh4] (8), while the previously reported complex [Ni2L 1 (1,3-N3)][ClO4] (2) of the 24-membered macrocycle (L 1 ) 2 coordinates it in the end-toend fashion. A comparison of the X-ray structures of 2, 3, and 7 reveals the form-selective binding of complex 3 to be a consequence of its pre-organized, channel-like binding pocket, which accommodates the azide anion via repulsive CH··· interactions in the end-on mode. In contrast to [Ni2L 1 (1,3-N3)][ClO4] (2), which features a S = 0 ground state, [Ni2(L2 )(1,1- N3)][BPh4] (8) has a S = 2 ground state that is attained by competing antiferromagnetic and ferromagnetic exchange interactions via the thiolato and azido bridges with a value for the magnetic exchange coupling constant J of 13 cm–1 (H = – 2JS1S2). These results are further substantiated by DFT calculations. The stability of the azido-bridged complex determined by isothermal titration calorimetry in MeCN/MeOH 1/1 v/v (log K11 = 4.88(4) at I = 0.1 M) lies in between those of the fluorido- (log K11 = 6.84(7)) and chlorido-bridged complexes (log K11 = 3.52(5)). These values were found to compare favorably well with the equilibrium constants derived at lower ionic strength (I = 0.01 M) by absorption spectrophotometry (log K11 = 5.20(1), 7.77(9), and 4.13(3) for N3 – , F– , and Cl– respectively).