The Magnetic Behaviour of CoTPP Supported on Coinage Metal Surfaces in the Presence of Small Molecules: A Molecular Cluster Study of the Surface trans-Effect

Density functional theory, combined with the molecular cluster model, has been used to investigate the surface trans-effect induced by the coordination of small molecules L (L = CO, NH3, NO, NO2 and O2) on the cobalt electronic structure of cobalt tetraphenylporphyrinato (CoTPP) surface-supported on coinage metal surfaces (Cu, Ag, and Au). Regardless of whether L has a closed- or an open-shell electronic structure, its coordination to Co takes out the direct interaction between Co and the substrate eventually present. The CO and NH3 bonding to CoTPP does not influence the Co local electronic structure, while the NO (NO2 and O2) coordination induces a Co reduction (oxidation), generating a 3d8 CoI (3d6 CoIII) magnetically silent closed-shell species. Theoretical outcomes herein reported demonstrate that simple and computationally inexpensive models can be used not only to rationalize but also to predict the effects of the Co–L bonding on the magnetic behaviour of CoTPP chemisorbed on coinage metals. The same model may be straightforwardly extended to other transition metals or coordinated molecules.

Effects of homoeologous exchange on gene expression and alternative splicing in a newly formed allotetraploid wheat

Homoeologous exchange (HE) is a major mechanism generating post-polyploidization genetic variation with important evolutionary consequences. However, the direct impacts of HE without entangling with additional evolutionary forces on gene expression remains to be fully understood. Here, we analyzed high-throughput RNA-seq data of young leaves from individuals of a synthetic allotetraploid wheat (AADD), which contain variable numbers of HEs. We aimed to investigate if and to which extent HE directly impacts gene expression and alternative splicing (AS). We found that HE impacts expression of genes located within HE regions primarily via cis-acting dosage effect, which led to significant changes in the total expression of homoeolog pairs, especially for homoeologs whose original expression was biased. In parallel, HE influences expression of a large amount of genes residing in non-HE regions by trans-regulation leading to convergent expression of homoeolog pairs. Intriguingly, when taking into account of the original relative homoeolog expression states, homoeolog pairs under trans-effect are more prone to showing convergent response to HE whereas those under cis-effect trended to show subgenome-specific expression. Moreover, HE induced quantitative, largely individual-specific, changes of alternative splicing (AS) events. Like homoeologs expression, homoeo-AS events which related to trans effect were more responsive to HE. HE therefore exerts multifaceted immediate effects on gene expression and, to a less extent, also transcript diversity in nascent allopolyploidy.

The Role of π–Donor/Acceptor trans Effect on The NO release in Ruthenium Nitrosyl Complexes: A Computational Insight

The nitric oxide (NO) molecule is associated to diverse biochemical routes. Ruthenium complexes are commonly used as model structures to control the NO availability. Here, the NO release mechanism in...

Synthesis, stability, and reactivity of mesoionic carbene iridium dihydride complexes

Pyridyl-triazolylidene ligands with variable donor properties were used as tunable ligands at a dihydride iridium(III) center. The straightforward synthesis of this type of ligand allows for an easy incorporation of electron donating substituents in different positions of the pyridine ring or different functional groups such as esters, alkoxy or aliphatic chains on the C4 position of the triazole heterocycle. The stability of these hydride metal systems allowed these complexes to be used as models for studying the influence of the ligand modifications on hydride reactivity. Spectroscopic analysis provided unambiguous structural assignment of the dihydride system. Modulation of the electronic properties of the wingtip substituents did not appreciably alter the reactivity of the hydrides. Reactivity studies using acids with a wide range of pKa values indicated a correlation between hydride reactivity and acidity and showed exclusive reactivity towards the less shielded hydride trans to the carbene carbon rather than the more shielded hydride trans to the pyridine ring, suggesting that the trans effect is more relevant in these reactions than the NMR spectroscopically deduced hydridic character.

Dioxygen at Biomimetic Single Metal-Atom Sites: Stabilization or Activation? The Case of CoTPyP/Au(111)

By means of a combined experimental and computational approach, we show that a 2D metal–organic framework self-assembled at the Au(111) termination is able to mimic the O2 stabilization and activation mechanisms that are typical of the biochemical environment of proteins and enzymes. 5,10,15,20-tetra(4-pyridyl)21H,23H-porphyrin cobalt(III) chloride (CoTPyP) molecules on Au(111) bind dioxygen forming a covalent bond at the Co center, yielding charge injection into the ligand by exploiting the surface trans-effect. A weakening of the O–O bond occurs, together with the development of a dipole moment, and a change in the molecule’s magnetic moment. Also the bonding geometry is similar to the biological counterpart, with the O2 molecule sitting on-top of the Co atom and the molecular axis tilted by 118°. The ligand configuration lays between the oxo- and the superoxo-species, in agreement with the observed O–O stretching frequency measured in situ at near-ambient pressure conditions.

Reactivity Studies of Cationic Au(III) Difluorides Supported by N-Ligands

The reactivity of difluoro Au(III) cations supported by pyridine or imidazole ligands is reported. The Au(III)-F bond is found to be susceptible to metathesis by TMS reagents and reagents bearing acidic protons such as H-CC-Ph and HOAc. In the latter case the reactions are slower than analogous reactions reported by other groups where strong -trans donors are present opposite the Au-F bond. This, coupled with the inability to effect metathesis on only one Au-F bond in our system indicates the -trans effect is a key consideration in Au-F chemistry

Reactivity Studies of Cationic Au(III) Difluorides Supported by N-Ligands

The reactivity of difluoro Au(III) cations supported by pyridine or imidazole ligands is reported. The Au(III)-F bond is found to be susceptible to metathesis by TMS reagents and reagents bearing acidic protons such as H-CC-Ph and HOAc. In the latter case the reactions are slower than analogous reactions reported by other groups where strong -trans donors are present opposite the Au-F bond. This, coupled with the inability to effect metathesis on only one Au-F bond in our system indicates the -trans effect is a key consideration in Au-F chemistry