Influence of the phonon-bottleneck effect and low-energy vibrational modes on the slow spin-phonon relaxation in Kramers-ions-based Cu(II) and Co(II) complexes with 4-amino-3,5-bis-(pyridin-2-yl)-1,2,4-triazole and dicyanamide.

Two new complexes, bis-[4-amino-3,5-bis-(pyridin-2-yl)-1,2,4-triazole-κ2N2,N6]bis-(dicyanamide-κN8)copper(II), [Cu(abpt)2(dca)2] (1) and bis-[4-amino-3,5-bis-(pyridin-2-yl)-1,2,4-triazole-κ2N2,N6]bis-(dicyanamide-κN8)cobalt(II), [Co(abpt)2(dca)2] (2), have been prepared and magneto-structurally characterised. Single crystal studies of both complexes have shown that their crystal structures are molecular, in which the central atoms are six-coordinated in the form of a distorted octahedron by two bidentate abpt and two monodentate dca ligands. Even if both complexes have the same composition and crystallize in the same P1̄ space group, they are not isostructural. Both structures contain strong intermolecular N-H⋯N hydrogen bonds and π-π stacking interactions. IR spectra are consistent with the solved structures of both complexes and confirmed the terminal character of the dca ligands and the bidentate coordination of the abpt ligands. The analysis of the magnetic properties showed that both complexes exhibit field-induced slow spin-phonon relaxation. In both complexes, the slow spin-phonon relaxation is influenced by a severe phonon-bottleneck effect that affects the direct process, a dominant relaxation mechanism at low temperatures in both complexes. The phonon-bottleneck effect in 1 was suppressed by simply reducing the crystallite size, and further analysis of the field dependence of the relaxation time yielded the characteristic energy of vibrational modes of 11 cm-1 participating in the Raman process at low magnetic fields. The analysis of magnetic properties and ab initio calculations confirmed that 2 represents a system with a moderate uniaxial anisotropy yielding an average energy barrier of 82 cm-1 (from all four nonequivalent Co(II) sites in the structure of 2).

Stabilization of Pancake Bonding in (TCNQ)2 .- Dimers in the Radical-Anionic Salt (N-CH3-2-NH2-5Cl-Py)(TCNQ)(CH3CN) Solvate and Antiferromagnetism Induction.

We report a new antiferromagnetic radical-anion salt (RAS) formed from 7,7,8,8-tetracyanquinonedimethane (TCNQ) anion and 2-amino-5-chloro-pyridine cation with the composition of (N-CH3-2-NH2-5Cl-Py)(TCNQ)(CH3CN). The crystallographic data indicates the formation of (TCNQ)2 .- radical-anion π-dimers in the synthesized RAS. Unrestricted density functional theory calculations show that the formed π-dimers characterize with strong π-stacking "pancake" interactions, resulting in high electronic coupling, enabling efficient charge transfer properties, but π-dimers cannot be stable in the isolated conditions as a result of strong Coulomb repulsions. In a crystal, where (TCNQ)2 .- π-dimers bound in the endless chainlets via supramolecular bonds with (N-CH3-2-NH2-5-Cl-Py)+ cations, the repulsion forces are screened, allowing for specific parallel π-stacking interactions and stable radical-anion dimers formation. Measurements of magnetic susceptibility and magnetization confirm antiferromagnetic properties of RAS, what is in line with the higher stability of ground singlet state of the radical-anion pair, calculated by means of the DFT. Therefore, the reported radical-anion (N-CH3-2-NH2-5Cl-Py)(TCNQ)(CH3CN) solvate has promising applications in novel magnetics with supramolecular structures.

A CuII complex with an carbamoylcyanonitrosomethanide ligand formed in situ by the nucleophilic addition of water to dicyanonitrosomethanide: structure, spectral and magnetic properties.

The complex (2,2'-biquinoline-κ2N,N')(carbamoylcyanonitrosomethanide-κ2N,O)chloridocopper(II) acetonitrile monosolvate, [Cu(C3H2N3O2)Cl(C18H12N2)]·CH3CN or [Cu(ccnm)Cl(biq)]·acn (acn is acetonitrile, biq is 2,2'-biquinoline and ccnm is carbamoylcyanonitrosomethanide), (I), was prepared as a result of nucleophilic addition of water to the dicyanonitrosomethanide ion in the presence of CuII and biq. IR spectroscopy confirmed the presence of ccnm, biq and acn in (I). The solid-state structure consists of the neutral complex containing ccnm and biq ligands, coordinated to the CuII atom in a bidendate chelating manner, and a chloride ligand, resulting in a distorted tetragonal pyramidal coordination of CuII. The asymmetric unit is supplemented by one molecule of solvated acn which, along with the nitrile group of ccnm, serves as an acceptor in intermolecular hydrogen bonding, creating infinite chains along the b axis. Magnetic measurements revealed a paramagnetic behaviour with a very small Weiss temperature Θ = -0.32 K and high anisotropy of the g tensor (gx = 2.036, gy = 2.120 and gz = 2.205).