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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Luminescence properties of heterodinuclear Pt_Eu complexes from unusual nonadentate ligands
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Luminescence properties of heterodinuclear Pt_Eu complexes from unusual nonadentate ligands

机译：不同寻常的非齿配体的异双核Pt_Eu配合物的发光特性

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摘要

The synthesis of ligand L_1, based on the tetramethyl ester of [4'-ethynyl-(6,6"-bis(aminomethyl))_2,2':6',2"-terpyridine]tetrakisacetate, and its acidic form L_2, are described. Using a Cu-assisted coupling reaction, L_1 was connected to the Pt atom of a [(tpy)Pt] precursor (tpy = 2,2':6',2"-terpyridine) to afford the [(tpy)PtL_1](BF_4) metallosynthon, from which a hydrolysis reaction gave Na_3[(tpy)PtL_2]. The photophysical properties of the metallosynthons were studied by means of absorption and steady state emission spectroscopic techniques in various solvents, which revealed a dramatic impact of the solvent polarity. DFT and TDDFT calculations (B3LYP) were used to investigate the absorption and emission properties of the [(tpy)PtL_1]_+ system both in vacuo and in different solvents. Spectrophotometric titrations of [(tpy)PtL_1]_+ with EuCl_3_6H_2O in acetonitrile revealed the formation of complicated mixtures of complexes with different [(tpyPtL_1)_xEu_y] stoichiometries, all of which display the typical Eu~(III) centred luminescence upon excitation into the Pt centred ~1MLCT absorption band. The energy transfer from the Pt subunit of [(tpy)PtL_2]~(3-) to Eu~(III) is inefficient in polar solvents, but it is restored in a TFA_CH_2Cl_2 mixture, together with the observation of a new emission band at 684 nm, likely arising from a charge transfer process involving reduction of Eu~(III)
机译：基于[4'-乙炔基-（6,6“-双（氨基甲基））_ 2,2'：6'，2”-吡啶基]四乙酰乙酸的四甲酯及其酸性形式的配体L_1的合成，描述。使用Cu辅助偶联反应，将L_1连接到[（tpy）Pt]前体的Pt原子（tpy = 2,2'：6'，2“-吡啶）得到[（tpy）PtL_1]（ BF_4）金属合成子，经水解反应生成Na_3 [（tpy）PtL_2]，利用吸收和稳态发射光谱技术研究了金属合成子在不同溶剂中的光物理性质，揭示了溶剂极性的显着影响。 DFT和TDDFT计算（B3LYP）用于研究[（tpy）PtL_1] _ +系统在真空和不同溶剂中的吸收和发射性质。用EuCl_3_6H_2O在乙腈中分光光度滴定[（tpy）PtL_1] _ +揭示了具有不同[（tpyPtL_1）_xEu_y]化学计量的配合物的复杂混合物的形成，当激发到以Pt为中心的〜1MLCT吸收带时，所有这些都显示出以Eu〜（III）为中心的典型发光。 [（tpy）PtL_2]〜（3-）至Eu〜（III）在极性溶剂中效率低下，但在TFA_CH_2Cl_2混合物中会被还原，并在684 nm处观察到新的发射带，这可能是由于涉及Eu〜（III）还原的电荷转移过程引起的

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