Dalton Transactions Blog

This HOT article by Mukherjee et al. reports the synthesis, structure, magnetic properties and DFT studies of four Cu(II)-azide polymers. Cu(II)-azide polymers are presently  being studied by many groups due to their interesting structural variation and magnetic properties. In this paper, three out of the four compounds studied are of new structural topologies.  All four complexes exhibit an overall ferromagnetic behaviour; the magnetic results are corroborated by DFT studies. The structural analysis shows how a simple change in the structure of the blocking ligand can generate entirely different structures and magnetic properties, even though the basic structures seems to be almost identical. It is also shown that another blocking diamine does not produce similar complexes under the same reaction conditions, which leads to the question: are certain compositions forbidden?

Read more about forbidden compositions and magnetic behaviour for FREE until the 2nd November at:
Cu^II-azide polymers with various molar equivalents of blocking diamine ligands: synthesis, structures, magnetic properties with DFT studies
Sandip Mukherjee, Yogesh P. Patil and Partha Sarathi Mukherjee
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11312G

Frank Neese (Max Planck) and Serena DeBeer (Cornell University), predict iron K-edge XAS pre-edge features for iron complexes using time-dependent density functional theory in this Dalton Transactions Hot article.

This work is building on the teams earlier investigations into ferrous and ferric complexes. The group will use their improved understanding of high valent iron intermediates to explain more about the behaviour of metalloproteins, and in this case they look at the heme active site of P450.

This paper is part of a themed issue guest edited by Stuart MacGregor (Heriot-Watt) on Computational Chemistry of Molecular Inorganic Systems that will be published online in the next few weeks. Make sure you hear about it by signing up to the Dalton Transactions table of contents e-alerts.

Read the full article for FREE  until 8th November to find out more about the use of X-ray absorption spectroscopy to understand metalloproteins…

Prediction of high-valent iron K-edge absorption spectra by time-dependent Density Functional Theory
P. Chandrasekaran, S. Chantal E. Stieber, Terrence J. Collins, Lawrence Que, Jr., Frank Neese and Serena DeBeer
Dalton Trans., 2011, DOI: 10.1039/C1DT11331C

In this HOT article, Constantinos J. Milios and co-workers describe the synthesis, crystal structures and magnetic properties of (a hexanuclear and an octanuclear) manganese(III) complexes based on a new oxime ligand, 2-dihydroxy-2-phenylacetamidine.  This is the first time that this ligand has been  used for the synthesis of polynuclear complexes of any transition metal ion. Even though the hexanuclear complex resembles the previously reported [Mn₆] clusters with salicyl-based oximes, the octanuclear complex presents a new structural type in Mn chemistry. Both complexes display moderate spin ground states (S = 3). The authors believe this new ligand is a promising candidate for a new extended family of manganese complexes with interesting magnetic properties and as impressive structures as its parent salicyl- or pyridyl-based oxime ligands.

Read more about this new ligand and potential magnetic properties for FREE until 25 th October at:

A new oxime ligand in manganese chemistry: a [Mn₈] and a [Mn₆] cage from the use of 2-dihydroxy-2-phenylacetamidine
Andreas G. Flamourakis, Demetrios Tzimopoulos, Milosz Siczek, Tadeusz Lis, James R. O’Brien, Pericles D. Akrivos and Constantinos J. Milios
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11455G