Structure and Bonding in Nickel-Thiolate-Iodine Charge-Transfer Complexes.

The dinuclear nickel complexes [Ni2 L(µ-O2 CR)](ClO4 ) [R=Me (4), R=OMe (6)], where L2- is a 24-membered macrocyclic N6 S2 ligand, react readily with excess I2 in MeCN solution at 4 °C to form stable mono-(I2 ) and bis-(I2 ) charge-transfer (CT) adducts of the type [Ni2 L(µ-O2 CR)(I2 )n ]+ (n=1 or 2) containing linear RS-I-I linkages. Three new CT compounds, namely, [Ni2 L(OAc)(I2 )](I2 )(I3 ) (5), [Ni2 L(O2 COMe)(I2 )](I5 )⋅MeCN (7⋅MeCN), and [Ni2 L(O2 COMe)(I2 )2 ](I5 )⋅MeCN (8⋅MeCN) as well as the triiodide salt [Ni2 L(OAc)](I3 ) (9) were synthesized and fully characterized. A common feature of the CT adducts is a polyiodide matrix, which surrounds the individual complex molecules, stabilized by secondary I⋅⋅⋅I interactions with the CT linkages. The scatter in both the RS-I (2.6 to 3.0 Å) and the I-I bond lengths (2.7 to 3.0 Å) is indicative of both a variable strength of the RS- →I2 bond and a varying degree of charge transfer. An analysis of the structural parameters was undertaken accompanied by DFT calculations to quantify the donating ability of the bridging thiolate functions and to shed more light on the bonding in this rare sort of charge-transfer complexes. The stability of the CT complexes and the results of preliminary transport measurements are also reported.

Adsorption of I2 by macrocyclic polyazadithiophenolato complexes mediated by charge-transfer interactions.

The macrocyclic complex [Ni2(L)(OAc)]ClO4 (1) adsorbs up to 17 molar equivalents (>270 wt%) of iodine, although it does not exhibit permanent porosity. Vibrational spectroscopic and crystallographic studies reveal that two I2 molecules are captured by means of thiophenolate→I2 charge-transfer interactions, which enable the diffusion and sorption of further I2 molecules in a polyiodide-like network. The efficient sorption and desorption characteristics make this material suitable for accommodation, sensing, and slow release of I2.

Interplay of magnetic exchange interactions and Ni-S-Ni bond angles in polynuclear nickel(II) complexes.

The ability of bridging thiophenolate groups (RS(-)) to transmit magnetic exchange interactions between paramagnetic Ni(II) ions is examined. Specific attention is paid to complexes with large Ni-SR-Ni angles. For this purpose, dinuclear [Ni(2)L(1)(mu-OAc)I(2)][I(5)] (2) and trinuclear [Ni(3)L(2)(OAc)(2)][BPh(4)](2) (3), where H(2)L(1) and H(2)L(2) represent 24-membered macrocyclic amino-thiophenol ligands, are prepared and fully characterized by IR- and UV/Vis spectroscopy, X-ray crystallography, static magnetization M measurements and high-field electron spin resonance (HF-ESR). The dinuclear complex 2 has a central N(3)Ni(2)(mu-S)(2)(mu-OAc)Ni(2)N(3) core with a mean Ni-S-Ni angle of 92 degrees . The macrocycle L(2) supports a trinuclear complex 3, with distorted octahedral N(2)O(2)S(2) and N(2)O(3)S coordination environments for one central and two terminal Ni(II) ions, respectively. The Ni-S-Ni angles are at 132.8 degrees and 133.5 degrees . We find that the variation of the bond angles has a very strong impact on the magnetic properties of the Ni complexes. In the case of the Ni(2)-complex, temperature T and magnetic field B dependencies of M reveal a ferromagnetic coupling J=-29 cm(-1) between two Ni(II) ions (H=JS(1)S(2)). HF-ESR measurements yield a negative axial magnetic anisotropy (D<0) which implies a bistable (easy axis) magnetic ground state. In contrast, for the Ni(3)-complex we find an appreciable antiferromagnetic coupling J'=97 cm(-1) between the Ni(II) ions and a positive axial magnetic anisotropy (D>0) which implies an easy plane situation.