Synthesis, structure and magnetic properties of mono- and di-nuclear nickel(II) thiocyanate complexes with tridentate N3 donor Schiff bases

The 1:1 condensation of N-methyl-1,3-diaminopropane and N,N-diethyl-1,2-diminoethane with 2-acetylpyridine, respectively at high dilution gives the tridentate mono-condensed Schiff bases N-methyl-N'-(1-pyridin-2-yl-ethylidene)-propane-1,3-diamine (L-1) and N,N-diethyl-N'-(1-pyridin-2-yl-ethylidene)-ethane-1,2-diamine (L-2). The tridentate ligands were allowed to react with methanol solutions of nickel(II) thiocyanate to prepare the complexes [Ni(L-1)(SCN)(2)(OH2) (1) and [{Ni(L-2)(SCN)}(2)] (2). Single crystal X-ray diffraction was used to confirm the structures of the complexes. The nickel(II) in complex 1 is bonded to three nitrogen donor atoms of the ligand L-1 in a mer orientation, together with two thiocyanates bonded through nitrogen and a water molecule, and it is the first Schiff base complex of nickel(II) containing both thiocyanate and coordinated water. The coordinated water initiates a hydrogen bonded 2D network. In complex 2, the nickel ion occupies a slightly distorted octahedral coordination sphere, being bonded to three nitrogen atoms from the ligand L-2, also in a mer orientation, and two thiocyanate anions through nitrogen. In contrast to 1, the sixth coordination site is occupied by a sulfur atom from a thiocyanate anion in an adjacent molecule, thus creating a centrosymmetric dimer. A variable temperature magnetic study of complex 2 indicates the simultaneous presence of zero-field splitting, weak intramolecular ferromagnetic coupling and intermolecular antiferromagnetic interactions between the nickel(II) centers.

The resolution sensitivity of the South Asian monsoon and Indo-Pacific in a global 0.35◦ AGCM

The South Asian monsoon is one of the most significant manifestations of the seasonal cycle. It directly impacts nearly one third of the world’s population and also has substantial global influence. Using 27-year integrations of a high-resolution atmospheric general circulation model (Met Office Unified Model), we study changes in South Asian monsoon precipitation and circulation when horizontal resolution is increased from approximately 200 to 40 km at the equator (N96 to N512, 1.9 to 0.35◦). The high resolution, integration length and ensemble size of the dataset make this the most extensive dataset used to evaluate the resolution sensitivity of the South Asian monsoon to date. We find a consistent pattern of JJAS precipitation and circulation changes as resolution increases, which include a slight increase in precipitation over peninsular India, changes in Indian and Indochinese orographic rain bands, increasing wind speeds in the Somali Jet, increasing precipitation over the Maritime Continent islands and decreasing precipitation over the northern Maritime Continent seas. To diagnose which resolution related processes cause these changes we compare them to published sensitivity experiments that change regional orography and coastlines. Our analysis indicates that improved resolution of the East African Highlands results in the improved representation of the Somali Jet and further suggests that improved resolution of orography over Indochina and the Maritime Continent results in more precipitation over the Maritime Continent islands at the expense of reduced precipitation further north. We also evaluate the resolution sensitivity of monsoon depressions and lows, which contribute more precipitation over northeast India at higher resolution. We conclude that while increasing resolution at these scales does not solve the many monsoon biases that exist in GCMs, it has a number of small, beneficial impacts.