Influence of electron donor and acceptor substituents on the excited state properties of rhenium(I) tetracarbonyl chelate complexes

Vanhelmont, Frederik W. M.; Rajasekharan, Melath V.; Güdel, Hans U.; Capelli, Silvia C.; Hauser, Jürg; Bürgi, Hans‐Beat

doi:10.1039/a803465f

Cited by 17 publications

(9 citation statements)

References 36 publications

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“…The ligands meodap and meobis , synthesized for the first time, have two methoxy groups in positions 5 and 8, and 6 and 6′, respectively. This substitution should influence the π‐acceptor properties of these ligands; reduced stabilities of meodap and meobis complexes were expected 45…”

Section: Methodsmentioning

confidence: 99%

Quantifying the Effect of Surface Ligands on Dendron–DNA Interactions: Insights into Multivalency through a Combined Experimental and Theoretical Approach

Jones

Pavan

Danani

et al. 2010

Chemistry A European J

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We report the synthesis, DNA binding ability and preliminary gene delivery profiles of dendrons with different amine surface groups, 1,3-diaminopropane (DAP), N,N-di-(3-aminopropyl)-N-(methyl)amine (DAPMA) and spermine (SPM). By using a combination of ethidium bromide displacement, gel electrophoresis and transfection assays, it is shown that the dendrons with SPM groups are the most effective DNA binders, while the DAPMA-functionalised dendrons were the most effective systems for gene delivery (although the gene delivery profiles were still modest). In order to provide deeper insight into the experimental data, we performed a molecular dynamics simulation of the interactions between the dendrons and DNA. The results of these simulations demonstrated that, in general terms, the enthalpic contribution to binding was roughly proportional to the dendron surface charge, but that dendrons with DAP (and DAPMA) surface amines had significant entropic costs of binding to DNA. In the case of DAP, this is a consequence of the fact that the entire dendron structure has to be organised in order for each individual monoamine charge to make effective contact with DNA. For SPM, however, each surface ligand is already a multivalent triamine, therefore, each individual charge has a much lower entropic cost of binding. For DAPMA, we observed that strong binding of the hindered tertiary amine to the DNA double helix led to ligand back-folding and significant geometric distortion of DNA. Although this weakens the overall binding, we suggest that this distortion might be an explanation for the experimentally observed enhanced gene delivery, in which DNA compaction is an important step. Overall, this paper demonstrates how structure-activity relationships can be developed for multivalent dendritic ligands and provides insights into the thermodynamics of multivalent interactions.

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Section: Methodsmentioning

confidence: 99%

Quantifying the Effect of Surface Ligands on Dendron–DNA Interactions: Insights into Multivalency through a Combined Experimental and Theoretical Approach

Jones

Pavan

Danani

et al. 2010

Chemistry A European J

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“…A CH 3 group on the ortho position of the pyridine ring has only little impact on the excited state properties. 216 Lifetimes are generally short, about 100 ms at 10 K. Despite the fact that iron plays a prominent role in many biological C-H bond activation processes, studies on cyclometalation using iron have remained remarkably scarce. While the first reports on iron-mediated C-H bond activation were amongst the first reports on cyclometalation generally, 219,220 the reaction has never been widely applied.…”

Section: Scheme 35mentioning

confidence: 99%

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

2009

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“…provide interesting strongly phosphorescent non-ionic materials. Some of them have already been demonstrated to be attractive for the electro (OLEDs) [13,[16][17][18][19][20][21] and the electrochemically generated luminescence (ECL) [22][23][24].The above-mentioned N \ C À ligands form stable chelates also with other transition metal ions including Pt(II) [25], Mn(I) [26] and Re(I) [27][28][29]. The present work deals with the physico-chemical properties of a new orthocyclometalated tetracarbonyl Re(I) chelate, the product of the reaction of 2-phenyl-benzothiazole (HUBT) with Re(CO) 5 Cl:…”

mentioning

confidence: 98%

“…The above-mentioned N \ C À ligands form stable chelates also with other transition metal ions including Pt(II) [25], Mn(I) [26] and Re(I) [27][28][29]. The present work deals with the physico-chemical properties of a new orthocyclometalated tetracarbonyl Re(I) chelate, the product of the reaction of 2-phenyl-benzothiazole (HUBT) with Re(CO) 5 Cl:…”

mentioning

confidence: 98%

A new cyclometalated rhenium(I) complex

Czerwieniec

Kapturkiewicz

Nowacki

2005

Inorganic Chemistry Communications

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Influence of electron donor and acceptor substituents on the excited state properties of rhenium(I) tetracarbonyl chelate complexes

Cited by 17 publications

References 36 publications

Quantifying the Effect of Surface Ligands on Dendron–DNA Interactions: Insights into Multivalency through a Combined Experimental and Theoretical Approach

Quantifying the Effect of Surface Ligands on Dendron–DNA Interactions: Insights into Multivalency through a Combined Experimental and Theoretical Approach

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

A new cyclometalated rhenium(I) complex

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