Dalton Transactions Blog

Unique cooperation has been observed between rhenium atoms and non-innocent N-confused porphyrin ligands in new oxorhenium(V) complexes.

The simplest porphyrin, porphine (left), and the N-confused porphyrin used to synthesize unique oxorhenium complexes.

Hiroyuki Furuta et al. have synthesised two new porphyrin oxorhenium(V) complexes which have been shown to be remarkably effective at oxygen atom transport. Through a catalytic process the oxygen atom from pyridine N-oxide can be transferred to PPh₃ in a 97% yield, notably higher than that of some other rhenium(V) complexes. The authors propose that the reason for their success is the existence of a Re-C bond, believing that this bond is important for efficient oxygen transport.

Atom transport is at the heart of successful catalysis, and as usual nature has already beaten us to it. Galactose oxidase for example converts a primary alcohol into an aldehyde by transporting a hydrogen atom from one part of the enzyme to another. But if the oxygen atom transfer seen in these synthetic N-confused porphyrin oxorhenium(V) complexes can be extended to other systems, exciting advancements in the field of catalysis could be on the horizon.

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To find out more about these exciting new complexes and the atom transport they facilitate, take a look at the full Dalton Transactions communication.

Cooperation between metal and ligand in oxygen atom transport by N-confused porphyrin oxorhenium(V) complexes
Takaaki Yamamoto, Motoki Toganoh and Hiroyuki Furuta

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By Katie Renouf, Web Writer

The team expected the assembly to form a helicate rather than catenate structure

Predicting the structure of large self-assembled units can become very complicated very quickly. Yet it is important for the rational design of new structures to understand how they assemble so new arrangements can be designed, with functional and valuable properties.

This Hot Article from the Piguet group investigates whether a pyridyl-benzimidazole ligand forms a double stranded helicate or a catenated architecture. The thermodynamic approach used to investigate the structures throws up some interesting results.

Looking for the origin of the switch between coordination-captured helicates and catenates
Lilit Aboshyan-Sorgho, Martine Cantuel, Gérald Bernardinelli and Claude Piguet
DOI: 10.1039/C2DT30414G

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Devices that store information magnetically are widespread, from the old floppy disks to credit cards and hard disks. The evolution of computer technologies requires us to continually develop new materials to allow new devices to out-perform their predecessors, for some time molecular spin cross-over complexes have been excellent candidates for new magnetic storage media.

Could mononuclear complexes in solution be the future of magnetic storage media?

This Hot Communication from Grace Morgan and colleagues details their developments in creating an Fe(III) complex which possesses magnetic hysteresis in solution. The authors note that spin cross over in some solid state materials is affected by polymorphism, counter ions and crystallisation solvents in the material. Find out more about the teams discoveries in solution by downloading their article while it is free…

Inducing hysteretic spin crossover in solution
Paulo N. Martinho, Yannick Ortin, Brendan Gildea, Claudio Gandolfi, George McKerr, Barry O’Hagan, Martin Albrecht and Grace G. Morgan
DOI: 10.1039/C2DT12036D

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The following articles might also be of interest;

A magnetic iron(III) switch with controlled and adjustable thermal response for solution processing
Claudio Gandolfi, Grace G. Morgan and Martin Albrecht
DOI: 10.1039/C2DT12037B

Synthesis and self-assembly of spin-labile and redox-active manganese(III) complexes
Claudio Gandolfi, Tatiana Cotting, Paulo N. Martinho, Olha Sereda, Antonia Neels, Grace G. Morgan and Martin Albrecht
DOI: 10.1039/C0DT01222J

Semiconductors are at the heart of nearly all things computerised, and with nearly all things computerised that makes semiconductors important. Semiconducting nanocrystals have become an interesting area of research because as colloidal inks they can potentially be used to easily print onto substrates to create photo-voltaic devices or a broad range of electronic devices.

CdSe nanocrystals undergoing ligand exchange and thermolysis

This Hot Communication from the Brutchey group details the use of a ligand which exchanges with the capping ligand of semiconducting CdSe nanocrystals making them highly dispersible in a range of polar solvents (in DMF a stable colloid forms for > 2 weeks). Under mild conditions thermolysis transforms the surface bound ligands to thiocyanate in situ, producing nanocrystal films of CdSe(SCN). There are also indications of improved inter-particle coupling…

Nanocrystal ligand exchange with 1,2,3,4-thiatriazole-5-thiolate and its facile in situ conversion to thiocyanate
David H. Webber and Richard L. Brutchey

This Hot Article is part of our up-coming themed issue ‘New Talent Americas’, Guest Edited by Dan Mindiola and John Arnold, other articles due to be published in this special issue include:

Perceiving Molecular Themes in the Structures and Bonding of Intermetallic Phases: The Role of Hückel Theory in an Ab Initio Era
Timothy E. Stacey and Daniel Fredrickson

Splitting water with rust: hematite photoelectrochemistry
Thomas W. Hamann

A heterobimetallic metal–organic framework with tunable reactive metal sites: synthesis, characterization, and reactivity
Nathan C. Smythe, Derek P. Butler, Curtis E. Moore, William R. McGowan, Arnold L. Rheingold and Laurance G. Beauvais