Versatile Para-Substituted Pyridine Lanthanide Coordination Complexes Allow Late Stage Tailoring of Complex Function.
Versatile Para-Substituted Pyridine Lanthanide Coordination Complexes Allow Late Stage Tailoring of Complex Function.
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DOI：
10.1002/chem.202103243
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发表时间：
2021-12-20
期刊：
影响因子：
--
通讯作者：
Parker D
中科院分区：
文献类型：
--
作者：
Starck M;Fradgley JD;De Rosa DF;Batsanov AS;Papa M;Taylor MJ;Lovett JE;Lutter JC;Allen MJ;Parker D
一系列阳离子和中性p-Br和p-NO2吡啶取代的Eu（III）和Gd（III）配合物作为多用途的合成中间体。亲核芳族取代在温和条件下容易在帕拉发生，允许C-N和C-C键形成反应发生，允许引入叠氮化物、氨基和炔基取代基。对于Eu（III）络合物，这种方法允许后期调谐吸收和发射光谱性质，例如通过降低伴随Eu-Npy键长减少的LMCT跃迁的能量。此外，这些配合物提供了直接获得相应的Eu（II）类似物的途径。对于Gd（III）系列，p-取代基的性质不会显著改变EPR性质（线宽、弛豫时间），这是它们作为EPR自旋探针开发所需的，其可以在温和条件下容易地与生物分子缀合。一系列阳离子和中性的对溴和对硝基吡啶取代的Eu（III）和Gd（III）配合物作为多用途的合成中间体。这种方法允许后期调谐的吸收和发射光谱性质的Eu（III）配合物，并提供了容易获得相应的Eu（II）类似物，有助于Gd（III）EPR自旋探针，可以很容易地共轭生物分子的发展，在温和的条件下。
A series of cationic and neutral p-Br and p-NO2 pyridine substituted Eu(III) and Gd(III) coordination complexes serve as versatile synthetic intermediates. Nucleophilic aromatic substitution occurs readily at the para position under mild conditions, allowing C–N and C–C bond forming reactions to take place, permitting the introduction of azide, amino and alkynyl substituents. For Eu(III) complexes, this approach allows late stage tuning of absorption and emission spectral properties, exemplified by the lowering of the energy of an LMCT transtion accompanied by a reduction in the Eu-Npy bond length. Additionally, these complexes provide direct access to the corresponding Eu(II) analogues. With the Gd(III) series, the nature of the p-substituent does not significantly change the EPR properties (linewidth, relaxation times), as required for their development as EPR spin probes that can be readily conjugated to biomolecules under mild conditions. A series of cationic and neutral p-bromo and p-nitropyridine substituted Eu(III) and Gd(III) coordination complexes serve as versatile synthetic intermediates. This approach allows the late stage tuning of absorption and emission spectroscopic properties for Eu(III) complexes, and provides easy access to the corresponding Eu(II) analogues, aiding the development of Gd(III) EPR spin probes that can be readily conjugated to biomolecules, under mild conditions.
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DOI：
10.1002/chem.202004450
发表时间：
2021-02-10
期刊：
Chemistry (Weinheim an der Bergstrasse, Germany)
影响因子：
--
作者：
Bailey MD;Jin GX;Carniato F;Botta M;Allen MJ
通讯作者：
Allen MJ
影响因子：
4.9
作者：
Gempf, Kathryn L.;Butler, Stephen J.;Parker, David
通讯作者：
Parker, David
影响因子：
--
作者：
Berry, MT;May, PS;Xu, H
通讯作者：
Xu, H
影响因子：
4.9
作者：
Sorensen, Thomas Just;Tropiano, Manuel;Faulkner, Stephen
通讯作者：
Faulkner, Stephen
影响因子：
1.8
作者：
Kalai, Tamas;Fleissner, Mark R.;Hideg, Kalman
通讯作者：
Hideg, Kalman