Carboxylic acid-tuned nickel(ii) clusters: syntheses, structures, solution behaviours and magnetic properties

Abstract

Three novel cicada-like nickel(II) clusters, formulated as [Ni₆(bdped)₂(mba)₆(Hdmpz)₂(NO₃)₂(H₂O)₂]·4MeCN (SD/Ni6b), [Ni₅(bdped)₂(tca)₆(Hdmpz)(MeOH)₂(H₂O)]·MeOH (SD/Ni5a) and [Ni₄(Hbdped)₂(ba)₄(Hdmpz)₂]·2NO₃·2MeCN (SD/Ni4a), were obtained by tuning the auxiliary carboxylic acids, where H₂bdped = 1,2-bis-(3,5-dimethylpyrazol-1-yl)-ethane-1,2-diol; Hmba = 2-methylbenzoic acid; Hdmpz = 3,5-dimethyl-1H-pyrazole; Htca = 3-thiophenecarboxylic acid; and Hba = benzoic acid. The structures of SD/Ni6b, SD/Ni5a and SD/Ni4a are built from a central Ni₄O₄ opened cube, appending two to zero NiNO₅ octahedra. The solution behaviours of SD/Ni6b, SD/Ni5a and SD/Ni4a were studied in detail via an ESI-MS technique and their solution stabilities were confirmed. Magnetic analysis indicated the presence of Ising-type anisotropy: D = −13, −10, and −11 cm⁻¹ for SD/Ni6b, SD/Ni5a, and SD/Ni4a, respectively; moreover, dominantly ferromagnetic interactions were found between magnetic centers: J₁ = 6.5 cm⁻¹, J₂ = −0.44 cm⁻¹ and J₁ = 5.9 cm⁻¹, J₂ = 2.6 cm⁻¹ for SD/Ni5a and SD/Ni4a, respectively. Besides, the photocurrent signals were observed and they reached the maximum very quickly for these three nickel(II) clusters and then their current intensities remained almost constant, which provide a possibility to be used for light-harvesting and photo-related catalysis.