A comparison of the gas, solution, and solid state coordination environments for the Cu(II) complexes of a series of linear aminopyridine ligands with varying ratios of 5- and 6-membered chelate rings

Hartman, Judith Ann R.; Kammier, Amanda L; Spracklin, Robert J; Pearson, Wayne H.; Combariza, Marianny Y.; Vachet, Richard W.

doi:10.1016/j.ica.2003.09.030

Cited by 27 publications

(16 citation statements)

References 46 publications

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“…The absence of the in-plane vibration at ca. 610 cm À1 for complexes 1 and 3 is consistent with the complexation of all the pyridinyl groups [20] with Cu 2 ion. PF À 6 Anions in complex 1 and ClO À 4 Anions in compounds 2 and 3 are characterized by broad and strong bands at ca.…”

Section: X-ray-diffraction Studies the Crystal Structures Of The Comsupporting

confidence: 80%

“…In the VIS region, complex 1 displays a single large and unsymmetric band at 680 nm with a low value of the molar extinction coefficient (e 70 m À1 cm À1 ). This spectrum closely resembles those of other six-coordinate CuN 6 chromophores [19] [20] and suggests a tetragonaldistorted octahedral geometry around the Cu 2 ion [22]. It must be noted that the spectrum of complex 1 in MeCN solution is completely different from the one obtained in the equilibrium studies for the [Cu(tpaa)] 2 species in aqueous solution, which is probably due to solvent-induced structural changes in aqueous solution.…”

Section: X-ray-diffraction Studies the Crystal Structures Of The Comsupporting

confidence: 62%

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Synthesis and Characterization of Copper Complexes Containing the Tripodal N₇ Ligand Tris{2‐[(pyridin‐2‐ylmethyl)amino]ethyl}amine (=N′‐(Pyridin‐2‐ylmethyl)‐N,N‐bis{2‐[(pyridin‐2‐ylmethyl)amino]ethyl}ethane‐1,2‐diamine): Equilibrium, Spectroscopic Data, and Crystal Structures of Mono‐ and Trinuclear Copper(II) Complexes

Gérard

Mohamadou

Marrot

et al. 2005

Helvetica Chimica Acta

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The stability constants of the Cu II chelates with the tripodal heptadentate ligand tris{2-[(2-pyridylmethyl)amino]ethyl}amine ( N'-(pyridin-2-ylmethyl)-N,N-bis{2-[(pyridin-2-ylmethyl)amino]ethyl}ethane-1,2-diamine; tpaa), determined by potentiometry and UV spectrometry, show the formation of [Cu(tpaaH)] 3 and [Cu(tpaa)] 2 species. In the solid state, two mononuclear Cu II compounds, [Cu(tpaa)](PF 6 ) 2 (1) and [Cu(tpaaH)](ClO 4 ) 3 ¥ H 2 O (2), and one trinuclear [Cu 3 (tpaa) 2 (ClO 4 ) 2 ](ClO 4 ) 4 ¥ 2 H 2 O (3) complex were isolated and characterized by IR, UV/VIS, and EPR spectroscopy. An X-ray structure of the mononuclear protonated complex 2 shows that the Cu 2 ion has a distorted square-pyramidal geometry (t 0.21). and the proton is bound to the secondary-amine function of one uncoordinated arm of the tripod ligand (Fig. 4). The crystal lattice for 2 is stabilized by the H-bonds between the N-atom of the free pyridinyl group with the proton of the free secondary-amine function of the neighboring molecule. The linear trinuclear complex 3 consists of two entities of the pyramidal mononuclear complex 1 bound to the third central Cu 2 ion by the free unprotonated arms of the ligands in equatorial position (Fig. 5). The octahedral geometry of the third Cu II atom is achieved by two perchlorate anions in the axial positions. The redox properties of 1 ± 3 compounds was examined by cyclic voltammetry.

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Section: X-ray-diffraction Studies the Crystal Structures Of The Comsupporting

confidence: 80%

Section: X-ray-diffraction Studies the Crystal Structures Of The Comsupporting

confidence: 62%

Synthesis and Characterization of Copper Complexes Containing the Tripodal N₇ Ligand Tris{2‐[(pyridin‐2‐ylmethyl)amino]ethyl}amine (=N′‐(Pyridin‐2‐ylmethyl)‐N,N‐bis{2‐[(pyridin‐2‐ylmethyl)amino]ethyl}ethane‐1,2‐diamine): Equilibrium, Spectroscopic Data, and Crystal Structures of Mono‐ and Trinuclear Copper(II) Complexes

Gérard

Mohamadou

Marrot

et al. 2005

Helvetica Chimica Acta

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“…Solution studies of the relative stability of copper complexes with various nitrogen ligands have been performed 9–14. Especially, the nitrogen heterocycles 1,10‐phenanthroline ( phen ), 2,2′‐bipyridine ( bpy ) and 2,9‐dimethyl‐1,10‐phenanthroline ( dmphen ) have been studied as chelate ligands in solution and by electrospray ionization mass spectrometry (ESI‐MS) in the gas phase 15–19…”

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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“…Selective reactions with different reagent gases can provide coordination number, but a more analytically convenient approach for determining this information is to use a single reagent that is capable of "titrating" the open coordination sites in a complex [14,34,35]. In this approach, the corresponding mass increase (or the absence of a mass increase) after the I-M reaction indicates the initial coordination number of the complex.…”

Section: Coordination Numbermentioning

confidence: 99%

Gas-phase ion–molecule reactions of divalent metal complex ions: Toward coordination structure analysis by mass spectrometry and some intrinsic coordination chemistry along the way

Combariza

Fahey

Milshteyn

et al. 2005

International Journal of Mass Spectrometry

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A comparison of the gas, solution, and solid state coordination environments for the Cu(II) complexes of a series of linear aminopyridine ligands with varying ratios of 5- and 6-membered chelate rings

Cited by 27 publications

References 46 publications

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

Gas-phase ion–molecule reactions of divalent metal complex ions: Toward coordination structure analysis by mass spectrometry and some intrinsic coordination chemistry along the way

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