Rhenium complexes of chromophore-appended dipicolylamine ligands: syntheses, spectroscopic properties, DNA binding and X-ray crystal structure
Rhenium complexes of chromophore-appended dipicolylamine ligands: syntheses, spectroscopic properties, DNA binding and X-ray crystal structure
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DOI：
10.1039/b800999f
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发表时间：
2008-12
影响因子：
3.3
通讯作者：
L. A. Mullice;R. H. Laye;Lindsay P. Harding;N. Buurma;Simon J. A. Pope
中科院分区：
文献类型：
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作者：
L. A. Mullice;R. H. Laye;Lindsay P. Harding;N. Buurma;Simon J. A. Pope
合成了两种含发色团的吡啶二胺衍生物配体，并研究了它们与五羰基氯铼的反应性。所得配合物各自具有fac-Re（CO）3核。通过一锅还原胺化反应以中等产率分离得到配体L111-[双（吡啶-2-基甲基）氨基]甲基芘和L22 - 2-[双（吡啶-2-基甲基）氨基]甲基喹喔啉。以良好的产率分离了相应的双金属配合物，并通过1H NMR，MS，IR和UV-Vis研究进行了表征。获得了fac-{Re（CO）3（L11）}（BF 4），C34 H26 BF 4 N4 O3 Re：单斜晶系，P2（1）/c，a = 18.327（2）A，α = 90.00°，B = 14.1537（14）A，β = 96.263（6）°，c = 23.511（3）A，γ = 90.00°，6062.4（11）A3，Z = 8.还研究了配体和配合物的发光性质，在每种情况下，发射归因于附加的发色团。等温滴定量热法表明，fac-{Re（CO）3（L11）}（BF 4）在水溶液中协同自聚集，研究了fac-{Re（CO）3（L11）}（BF 4）与DNA的结合特性，发现fac-{Re（CO）3（L11）}（BF 4）与鱼精子DNA的结合（结合常数1.5 ± 0.2 × 105 M−1，结合位点大小3.2 ± 0.3个碱基对）伴随着UV-Vis光谱的变化，如通常在基于芘的嵌入剂中观察到的，而量热测定的结合焓（−14 ± 2 kcal mol−1）也与通常在嵌入剂中发现的值一致。
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) A, α = 90.00°, b = 14.1537(14) A, β = 96.263(6)°, c = 23.511(3) A, γ = 90.00°, 6062.4(11) A3, 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.