Diverse Solid-State and Solution Structures within a Series of Hexaamine Dicopper(II) Complexes

Bernhardt, Paul V.

doi:10.1021/ic000928s

Cited by 21 publications

(14 citation statements)

References 32 publications

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“…The Cu (1) (2) is completed by bidentate coordination of the carbonato ligand. This  1 : 2 ,-CO 3 2− coordination mode has been observed in several complexes of copper(II) 33,35,36 and other transition ions. 37 Both copper ions have near-ideal square-pyramidal geometries according to their  parameters [0.172(4)/0.217 (6) for Cu(1), calculated from I(1) and O(1) respectively, and 0.019(4) for Cu (2)].…”

Section: Resultssupporting

confidence: 59%

Synthesis and coordination chemistry of 1,1,1-tris-(pyrid-2-yl)ethane

et al. 2015

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Section: Resultssupporting

confidence: 59%

Synthesis and coordination chemistry of 1,1,1-tris-(pyrid-2-yl)ethane

et al. 2015

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“…The monothiaz ( 5 ) can be easily purified using column chromatography from unreacted starting material, which can be isolated for later re-use. The monoamide ( 5 ) is then coupled to each of the amine backbones ( 6a–c ), synthesized according to literature procedures, 12 to yield the protected ligands ( 7a–c ). Removal of the remaining benzyl protecting groups was achieved under standard hydrogenation conditions to furnish the final desired ligands ( 8a–c ).…”

Section: Resultsmentioning

confidence: 99%

“…To a solution of 5 (1.94 g, 4.5 mmol) in CH 2 Cl 2 (100 mL) was added N,N,N',N'-tetrakis-(2-aminoethyl)-butane-1,4-diamine ( 6c ) 12 (0.26 g, 1 mmol) and the mixture was stirred for 9 h at room temperature. The reaction mixture was then evaporated to dryness and applied to a silica gel column.…”

Section: Methodsmentioning

confidence: 99%

“…This compound was prepared using a procedure analogous to that described for 7c above, substituting N,N,N',N'-tetrakis-(2-aminoethyl)-propane-1,3-diamine ( 6b ) 12 where appropriate, to yield the desired product as a white foam (83%): 1 H NMR (500 MHz, CDCl 3 ): δ 1.24 (q, 2H, J = 7 Hz, CH 2 ), 2.17 (t, 4H, J = 7 Hz, CH 2 ), 2.23 (t, 8H, J = 6 Hz, CH 2 ), 3.13 (q, J = 6 Hz, 8H, CH 2 ), 3.16 (s, 12H, OCH 3 ), 3.38 (t, J = 6 Hz, 8H, CH 2 ), 3.49 (q, 8H, J = 6 Hz, CH 2 ), 4.86 (s, 8H, OCH 2 ), 7.08 (t, J = 8 Hz, 4H, ArH), 7.30–7.40 (m, 20H, ArH), 7.53 (t, J = 6 Hz, 4H, NH), 7.63 (dd, J = 8 Hz, 2 Hz, 4H, ArH), 7.75 (t, 4H, J = 6 Hz, NH), 7.90 (t, J = 8 Hz, 2 Hz, 4H, ArH) ppm; 13 C NMR (125 MHz, CDCl 3 ): δ 37.4, 39.4, 51.4, 52.5, 53.3, 58.2, 70.3, 78.2, 124.4, 128.0, 128.2, 128.4, 128.5, 128.7, 133.0, 133.2, 135.2, 154.0, 165.0, 165.4 ppm; MS (FAB+): m/z 1492.7 [MH + ].…”

Section: Methodsmentioning

confidence: 99%

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Water-Soluble 2-Hydroxyisophthalamides for Sensitization of Lanthanide Luminescence

et al. 2008

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A series of octadentate ligands featuring the 2-hydroxyisophthalamide (IAM) antenna chromophore (to sensitize Tb(III) and Eu(III) luminescence) has been prepared and characterized. The length of the alkyl amine scaffold that links the four IAM moieties has been varied in order to investigate the effect of the ligand backbone on the stability and photophysical properties of the Ln(III) complexes. The amine backbones utilized in this study are N,N,N',N'-tetrakis-(2-aminoethyl)-ethane-1,2-diamine [H(2,2)-], N,N,N',N'-tetrakis-(2-aminoethyl)-propane-1,3-diamine [H(3,2)-] and N,N,N',N'-tetrakis-(2-aminoethyl)-butane-1,4-diamine [H(4,2)-]. These ligands also incorporate methoxyethylene [MOE] groups on each of the IAM chromophores to increase their water solubility. The aqueous ligand protonation constants and Tb(III) and Eu(III) formation constants were determined from solution thermodynamic studies. The resulting values indicate that at physiological pH, the Eu(III) and Tb(III) complexes of H(2,2)-IAM-MOE and H(4,2)-IAM-MOE are sufficiently stable to prevent dissociation at nanomolar concentrations. The photophysical measurements for the Tb(III) complexes gave overall quantum yield values of 0.56, 0.39, and 0.52 respectively for the complexes with H(2,2)-IAM-MOE, H(3,2)-IAM-MOE and H(4,2)-IAM-MOE, while the corresponding Eu(III) complexes displayed significantly weaker luminescence, with quantum yield values of 0.0014, 0.0015, and 0.0058, respectively. Analysis of the steady state Eu(III) emission spectra provides insight into the solution symmetries of the complexes. The combined solubility, stability and photophysical performance of the Tb(III) complexes in particular make them well suited to serve as the luminescent reporter group in high sensitivity time-resolved fluoroimmunoassays.

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“…The Cu II complexation of the oligosaccharide‐modified dendrimers 1 – 4 is based on the presence of six interior tertiary amino groups for 1 and 2 and 14 interior tertiary amino groups for 3 and 4 . According to the literature,13, 32–34 tertiary amino groups are also able to complex Cu II besides the well‐known complexation tendency of primary amino groups against Cu II . Therefore, the maltose‐ and maltotriose‐modified dendrimers 1 – 4 were used for the first complexation studies with Cu II by UV/vis spectroscopy in water.…”

Section: Resultsmentioning

confidence: 99%

Oligosaccharide‐Modified Poly(propyleneimine) Dendrimers: Synthesis, Structure Determination, and Cu^II Complexation

Appelhans

Zhong

Komber

et al. 2007

Macromolecular Bioscience

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The multiple application of reductive amination on primary amino groups of first and second generation poly(propyleneimine) dendrimers is used as a one-pot approach to introduce twice the amount of the oligosaccharide units as surface groups, compared to initially present amino groups in the first and second generation dendrimers. This was proven by (1)H NMR, MALDI-TOF-MS, and LILBID-MS analysis. The size of these dendrimers was determined by the hydrodynamic radius using pulsed field gradient NMR and dynamic light scattering. Molecular modeling confirmed the presence of dense-shell dendrimers. These dendrimers exhibit a generation dependent Cu(II)/dendrimer ratio in an aqueous environment, highlighting these materials as possible metal-carrier systems with a well-defined oligosaccharide protection shell for application in a biological environment.

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Diverse Solid-State and Solution Structures within a Series of Hexaamine Dicopper(II) Complexes

Cited by 21 publications

References 32 publications

Synthesis and coordination chemistry of 1,1,1-tris-(pyrid-2-yl)ethane

Synthesis and coordination chemistry of 1,1,1-tris-(pyrid-2-yl)ethane

Water-Soluble 2-Hydroxyisophthalamides for Sensitization of Lanthanide Luminescence

Oligosaccharide‐Modified Poly(propyleneimine) Dendrimers: Synthesis, Structure Determination, and Cu^II Complexation

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Diverse Solid-State and Solution Structures within a Series of Hexaamine Dicopper(II) Complexes

Cited by 21 publications

References 32 publications

Synthesis and coordination chemistry of 1,1,1-tris-(pyrid-2-yl)ethane

Synthesis and coordination chemistry of 1,1,1-tris-(pyrid-2-yl)ethane

Water-Soluble 2-Hydroxyisophthalamides for Sensitization of Lanthanide Luminescence

Oligosaccharide‐Modified Poly(propyleneimine) Dendrimers: Synthesis, Structure Determination, and CuII Complexation

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Product

Resources

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Oligosaccharide‐Modified Poly(propyleneimine) Dendrimers: Synthesis, Structure Determination, and Cu^II Complexation