2,11‐Dialkylated 1,12‐Diazaperylene Copper(I) Complexes: First Supramolecular Column Assemblies by π‐π Stacking between Homoleptic Tetrahedral Metal Complexes, Exhibiting Low‐Energy MLCT Transitions

Kämmer, Stefan; Kelling, Alexandra; Baier, Heiko; Mickler, Wulfhard; Dosche, Carsten; Rurack, Knut; Kapp, Andreas; Lisdat, Fred; Holdt, Hans‐Jürgen

doi:10.1002/ejic.200900695

Cited by 19 publications

(14 citation statements)

References 39 publications

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“…A synthetic goal has been to maximize the size of the substituents at positions 2 and 9 of the phenanthroline ligand, while retaining the two bidentate ligands on the metal center which give rise to the MLCT. Recently, a number of 2,11‐dialkylated 1,12‐diazaperlyenes [alkyl = methyl ( dmdap ), ethyl ( dedap ) and isopropyl ( dipdap )], have been synthesized by reductive cyclization of the corresponding 3,3′‐dialkylated 1,1′‐bisisoquinolines dmbis , debis , and dipbis which are the first copper(I) complexes with ‘large surface’ ligands 44…”

Section: Methodsmentioning

confidence: 99%

“…The ligands 1,12‐diazaperylene55 ( dap ) and bis(isoquinoline)56 ( bis ), and the 2,11‐dialkylated 1,12‐diazaperylene (alkyl = Me, ethyl, and isopropyl), were synthesized by reductive cyclization of the corresponding 3,3′‐dialkylated 1,1′‐bisisoquinolines. The 3,3′‐alkyl‐1,1′‐bisisoquinolines were synthesized by homocoupling the corresponding 1‐chloro‐3‐alkylisoquinolines 44…”

Section: Methodsmentioning

confidence: 99%

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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%

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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“…Metalla-supramolecular assemblies with honeycomb [11]. Tetrahedral copper(I) complexes with 2,11-dialkylated dap exhibit low-energy MLCT transitions [12]. A dirhodium dap complex with bridging acetato groups was found to have the dual capability of intercalative and coordinative binding to DNA [13].…”

Section: Commentmentioning

confidence: 99%

The crystal structure of 1,12-diazaperylene, C₁₈H₁₀N₂

Kirste

Brietzke

Holdt

et al. 2019

Zeitschrift Für Kristallographie - New Crystal Structures

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“…19,20 Recently, we described the synthesis of a wide range of diazaperylenes as large-surface ligands with increased π-delocalization and the corresponding flexible nonplanar bisisoquinolines. 21,22 These ligands are intensely studied chelating ligands in the coordination chemistry of transition metal ions. [23][24][25] Complex formation and stability of the ligands 1 to 12 (Scheme 1A) with various types of transition metal ions in the gas phase has been studied by us using ESI-MS and collision-induced dissociation (CID) measurements.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, we described the synthesis of a wide range of diazaperylenes as large‐surface ligands with increased π‐delocalization and the corresponding flexible nonplanar bisisoquinolines . These ligands are intensely studied chelating ligands in the coordination chemistry of transition metal ions .…”

Section: Introductionmentioning

confidence: 99%

Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline

et al. 2018

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The complex formation of the following diazaperylene ligands (L) 1,12-diazaperylene 1, 1,1'-bisisoquinoline 2, 2,11-disubstituted 1,12-diazaperylenes (alkyl = methyl, ethyl, isopropyl, 3, 5, 7), 3,3'-disubstituted 1,1'-bisisoquinoline (alkyl = methyl, ethyl, isopropyl, 4, 6, 8 and with R = phenyl, 11 and with pyridine 12), and the 5,8-dimethoxy-substituted diazaperylene 9, 6,6'-dimethoxy-substituted bisisoquinoline 10 with AgBF4 was investigated. Collision-induced dissociation measurements were used to evaluate the relative stabilities of the ligands themselves and for the [1:1] complexes as well as for the homoleptic and heteroleptic silver [1:2] complexes in the gas phase. This method is very useful in rapid screening of the stabilities of new complexes in the gas phase. The influence of the spatial arrangement of the ligands and the type of substituents employed for the complexation were examined. The effect of the preorganization of the diazaperylene on the threshold activation voltages and thus of the relative binding energies of the different complexes are discussed. Density functional theory calculations were used to calculate the optimized structures of the silver complexes and compared with the stabilities of the complexes in the gas phase for the first time.

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2,11‐Dialkylated 1,12‐Diazaperylene Copper(I) Complexes: First Supramolecular Column Assemblies by π‐π Stacking between Homoleptic Tetrahedral Metal Complexes, Exhibiting Low‐Energy MLCT Transitions

Cited by 19 publications

References 39 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

The crystal structure of 1,12-diazaperylene, C₁₈H₁₀N₂

Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline

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2,11‐Dialkylated 1,12‐Diazaperylene Copper(I) Complexes: First Supramolecular Column Assemblies by π‐π Stacking between Homoleptic Tetrahedral Metal Complexes, Exhibiting Low‐Energy MLCT Transitions

Cited by 19 publications

References 39 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

The crystal structure of 1,12-diazaperylene, C18H10N2

Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline

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The crystal structure of 1,12-diazaperylene, C₁₈H₁₀N₂