Rhenium complexes of chromophore-appended dipicolylamine ligands

Syntheses, spectroscopic properties, DNA binding and X-ray crystal structure

L.A. Mullice, R.H. Laye, L.P. Harding, N.J. Buurma, S.J.A. Pope

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

The syntheses of two chromophore-appended dipicolylamine-derived ligands and their reactivity with pentacarbonylchlororhenium have been studied. The resultant complexes each possess the fac-Re(CO)3 core. The ligands L111-[bis(pyridine-2-ylmethyl)amino]methylpyrene and L22 2-[bis(pyridine-2-ylmethyl)amino]methylquinoxaline were isolated via a one-pot reductive amination in moderate yield. The corresponding rhenium complexes were isolated in good yields and characterised by 1H NMR, MS, IR and UV-Vis studies. X-Ray crystallographic data were obtained for fac-{Re(CO)3(L11)}(BF4), C34H26BF4N4O3Re: monoclinic, P2(1)/c, a = 18.327(2) Å, α = 90.00°, b = 14.1537(14) Å, β = 96.263(6)°, c = 23.511(3) Å, γ = 90.00°, 6062.4(11) Å3, Z = 8. The luminescence properties of the ligands and complexes were also investigated, with the emission attributed to the appended chromophore in each case. Isothermal titration calorimetry suggests that fac-{Re(CO)3(L11)}(BF4) self-aggregates cooperatively in aqueous solution, probably forming micelle-like aggregates with a cmc of 0.18 mM. Investigations into the DNA-binding properties of fac-{Re(CO)3(L11)}(BF4) were undertaken and revealed that fac-{Re(CO)3(L11)}(BF4) binding to fish sperm DNA (binding constant 1.5 ± 0.2 × 105 M−1, binding site size 3.2 ± 0.3 base pairs) is accompanied by changes in the UV-Vis spectrum as typically observed for pyrene-based intercalators while the calorimetrically determined binding enthalpy (−14 ± 2 kcal mol−1) also agrees favourably with values as typically found for intercalators.
Original languageEnglish
Pages (from-to)2140-2149
Number of pages10
JournalNew Journal of Chemistry
Volume32
Issue number12
DOIs
Publication statusPublished - 22 Aug 2008

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Rhenium
Carbon Monoxide
Chromophores
DNA
Crystal structure
Ligands
X rays
Pyridine
Intercalating Agents
Amination
Pyrene
Calorimetry
Binding sites
Titration
Micelles
Fish
Luminescence
Enthalpy
Nuclear magnetic resonance
Binding Sites

Cite this

@article{2880fdcc3ad048b5ba3c9b48f874845a,
title = "Rhenium complexes of chromophore-appended dipicolylamine ligands: Syntheses, spectroscopic properties, DNA binding and X-ray crystal structure",
abstract = "The syntheses of two chromophore-appended dipicolylamine-derived ligands and their reactivity with pentacarbonylchlororhenium have been studied. The resultant complexes each possess the fac-Re(CO)3 core. The ligands L111-[bis(pyridine-2-ylmethyl)amino]methylpyrene and L22 2-[bis(pyridine-2-ylmethyl)amino]methylquinoxaline were isolated via a one-pot reductive amination in moderate yield. The corresponding rhenium complexes were isolated in good yields and characterised by 1H NMR, MS, IR and UV-Vis studies. X-Ray crystallographic data were obtained for fac-{Re(CO)3(L11)}(BF4), C34H26BF4N4O3Re: monoclinic, P2(1)/c, a = 18.327(2) {\AA}, α = 90.00°, b = 14.1537(14) {\AA}, β = 96.263(6)°, c = 23.511(3) {\AA}, γ = 90.00°, 6062.4(11) {\AA}3, Z = 8. The luminescence properties of the ligands and complexes were also investigated, with the emission attributed to the appended chromophore in each case. Isothermal titration calorimetry suggests that fac-{Re(CO)3(L11)}(BF4) self-aggregates cooperatively in aqueous solution, probably forming micelle-like aggregates with a cmc of 0.18 mM. Investigations into the DNA-binding properties of fac-{Re(CO)3(L11)}(BF4) were undertaken and revealed that fac-{Re(CO)3(L11)}(BF4) binding to fish sperm DNA (binding constant 1.5 ± 0.2 × 105 M−1, binding site size 3.2 ± 0.3 base pairs) is accompanied by changes in the UV-Vis spectrum as typically observed for pyrene-based intercalators while the calorimetrically determined binding enthalpy (−14 ± 2 kcal mol−1) also agrees favourably with values as typically found for intercalators.",
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Rhenium complexes of chromophore-appended dipicolylamine ligands : Syntheses, spectroscopic properties, DNA binding and X-ray crystal structure. / Mullice, L.A.; Laye, R.H.; Harding, L.P.; Buurma, N.J.; Pope, S.J.A.

In: New Journal of Chemistry, Vol. 32, No. 12, 22.08.2008, p. 2140-2149.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Rhenium complexes of chromophore-appended dipicolylamine ligands

T2 - Syntheses, spectroscopic properties, DNA binding and X-ray crystal structure

AU - Mullice, L.A.

AU - Laye, R.H.

AU - Harding, L.P.

AU - Buurma, N.J.

AU - Pope, S.J.A.

N1 - cited By 35

PY - 2008/8/22

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N2 - The syntheses of two chromophore-appended dipicolylamine-derived ligands and their reactivity with pentacarbonylchlororhenium have been studied. The resultant complexes each possess the fac-Re(CO)3 core. The ligands L111-[bis(pyridine-2-ylmethyl)amino]methylpyrene and L22 2-[bis(pyridine-2-ylmethyl)amino]methylquinoxaline were isolated via a one-pot reductive amination in moderate yield. The corresponding rhenium complexes were isolated in good yields and characterised by 1H NMR, MS, IR and UV-Vis studies. X-Ray crystallographic data were obtained for fac-{Re(CO)3(L11)}(BF4), C34H26BF4N4O3Re: monoclinic, P2(1)/c, a = 18.327(2) Å, α = 90.00°, b = 14.1537(14) Å, β = 96.263(6)°, c = 23.511(3) Å, γ = 90.00°, 6062.4(11) Å3, Z = 8. The luminescence properties of the ligands and complexes were also investigated, with the emission attributed to the appended chromophore in each case. Isothermal titration calorimetry suggests that fac-{Re(CO)3(L11)}(BF4) self-aggregates cooperatively in aqueous solution, probably forming micelle-like aggregates with a cmc of 0.18 mM. Investigations into the DNA-binding properties of fac-{Re(CO)3(L11)}(BF4) were undertaken and revealed that fac-{Re(CO)3(L11)}(BF4) binding to fish sperm DNA (binding constant 1.5 ± 0.2 × 105 M−1, binding site size 3.2 ± 0.3 base pairs) is accompanied by changes in the UV-Vis spectrum as typically observed for pyrene-based intercalators while the calorimetrically determined binding enthalpy (−14 ± 2 kcal mol−1) also agrees favourably with values as typically found for intercalators.

AB - The syntheses of two chromophore-appended dipicolylamine-derived ligands and their reactivity with pentacarbonylchlororhenium have been studied. The resultant complexes each possess the fac-Re(CO)3 core. The ligands L111-[bis(pyridine-2-ylmethyl)amino]methylpyrene and L22 2-[bis(pyridine-2-ylmethyl)amino]methylquinoxaline were isolated via a one-pot reductive amination in moderate yield. The corresponding rhenium complexes were isolated in good yields and characterised by 1H NMR, MS, IR and UV-Vis studies. X-Ray crystallographic data were obtained for fac-{Re(CO)3(L11)}(BF4), C34H26BF4N4O3Re: monoclinic, P2(1)/c, a = 18.327(2) Å, α = 90.00°, b = 14.1537(14) Å, β = 96.263(6)°, c = 23.511(3) Å, γ = 90.00°, 6062.4(11) Å3, Z = 8. The luminescence properties of the ligands and complexes were also investigated, with the emission attributed to the appended chromophore in each case. Isothermal titration calorimetry suggests that fac-{Re(CO)3(L11)}(BF4) self-aggregates cooperatively in aqueous solution, probably forming micelle-like aggregates with a cmc of 0.18 mM. Investigations into the DNA-binding properties of fac-{Re(CO)3(L11)}(BF4) were undertaken and revealed that fac-{Re(CO)3(L11)}(BF4) binding to fish sperm DNA (binding constant 1.5 ± 0.2 × 105 M−1, binding site size 3.2 ± 0.3 base pairs) is accompanied by changes in the UV-Vis spectrum as typically observed for pyrene-based intercalators while the calorimetrically determined binding enthalpy (−14 ± 2 kcal mol−1) also agrees favourably with values as typically found for intercalators.

U2 - 10.1039/b800999f

DO - 10.1039/b800999f

M3 - Article

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SP - 2140

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JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

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