当前位置：
X-MOL 学术
›
Organometallics
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
σ-Pt-BODIPY Complexes with Platinum Attachment to Carbon Atoms C2 or C3: Spectroscopic, Structural, and (Spectro)Electrochemical Studies and Photocatalysis
Organometallics ( IF 2.5 ) Pub Date : 2018-01-04 00:00:00 , DOI: 10.1021/acs.organomet.7b00806 Peter Irmler 1 , Rainer F. Winter 1
Organometallics ( IF 2.5 ) Pub Date : 2018-01-04 00:00:00 , DOI: 10.1021/acs.organomet.7b00806 Peter Irmler 1 , Rainer F. Winter 1
Affiliation
|
In this work we discuss five new complexes with the general formula trans-Pt(bodipy)I(PEt3)2, where differently substituted bodipy dyes attach to the coordination center via a direct Pt–C σ-bond to the pyrrolic carbon atom C2 or C3. We also report an isolable intermediate of the oxidative addition step where the bodipy is η2-bonded to the cis-Pt(0)(PEt3)2 moiety. Comparison between the new complexes, meso-platinated analogue 8-Pt, and the parent dyes reveals that the site of platinum attachment influences the spectroscopic, photophysical, electrochemical, and electronic properties. In contrast to 8-Pt, absorption and emission bands are red-shifted with respect to the parent dyes. 2-Platinated bodipy dyes 2-Pt-6H, 2-Pt-6I, 2-Pt-Mes-6I, and 2-Pt-6Et exhibit dual fluorescence and NIR phosphorescence emissions, with low quantum yields, whereas 3-Pt emits solely by fluorescence (ΦFl = 52.7%). The complexes are modestly efficient sensitizers for photochemical 1O2 production but outperform methylene blue. They also undergo one reversible one-electron reduction and oxidation as indicated by cyclic voltammetry. Half-wave potentials are cathodically shifted by 340–510 mV with respect to the parent dyes. The one-electron reduced and some of the one-electron oxidized forms were generated and investigated by UV/vis/NIR and EPR spectroscopy as well as TD-DFT calculations. The similarity of their spectra to those of the one-electron reduced or oxidized forms of other bodipy dyes as well as the richly structured EPR spectra and g-values close to ge attest to a dominant bodipy character of the relevant frontier MOs.
中文翻译：
铂与碳原子C2或C3结合的σ-Pt-BODIPY配合物：光谱，结构和（光谱）电化学研究和光催化作用
在这项工作中，我们讨论了五个具有通式反式-Pt（bodipy）I（PEt 3）2的新配合物，其中不同取代的bodipy染料通过直接Pt-Cσ-键与吡咯碳原子C2结合到配位中心。或C3。其中BODIPY是η我们还报告可分离的中间氧化加成步骤的2键合的所述顺式-Pt（0）（PET 3）2部分。新的配合物，内消旋的类似物8-Pt和母体染料之间的比较表明，铂的附着位置会影响光谱，光物理，电化学和电子性质。与之相反8-Pt的吸收带和发射带相对于母体染料发生红移。2-Platinated Bodipy染料2-Pt-6H，2-Pt-6I，2-Pt-Mes-6I和2-Pt-6Et表现出双重荧光和NIR磷光发射，量子产率低，而3-Pt仅发射通过荧光（Φ FL = 52.7％）。该络合物是光化学1 O 2的适度有效敏化剂。生产，但优于亚甲基蓝。如循环伏安法所示，它们还经历一种可逆的单电子还原和氧化。相对于母体染料，半波电势被阴极移动340–510 mV。生成了单电子还原形式和一些单电子氧化形式，并通过UV / vis / NIR和EPR光谱以及TD-DFT计算进行了研究。它们的光谱的那些的其他BODIPY染料的单电子还原或氧化形式以及相似度的丰富的结构EPR谱和克-值接近克Ë证实了有关前沿的MO的显性BODIPY字符。
更新日期：2018-01-05
中文翻译：
铂与碳原子C2或C3结合的σ-Pt-BODIPY配合物：光谱，结构和（光谱）电化学研究和光催化作用
在这项工作中，我们讨论了五个具有通式反式-Pt（bodipy）I（PEt 3）2的新配合物，其中不同取代的bodipy染料通过直接Pt-Cσ-键与吡咯碳原子C2结合到配位中心。或C3。其中BODIPY是η我们还报告可分离的中间氧化加成步骤的2键合的所述顺式-Pt（0）（PET 3）2部分。新的配合物，内消旋的类似物8-Pt和母体染料之间的比较表明，铂的附着位置会影响光谱，光物理，电化学和电子性质。与之相反8-Pt的吸收带和发射带相对于母体染料发生红移。2-Platinated Bodipy染料2-Pt-6H，2-Pt-6I，2-Pt-Mes-6I和2-Pt-6Et表现出双重荧光和NIR磷光发射，量子产率低，而3-Pt仅发射通过荧光（Φ FL = 52.7％）。该络合物是光化学1 O 2的适度有效敏化剂。生产，但优于亚甲基蓝。如循环伏安法所示，它们还经历一种可逆的单电子还原和氧化。相对于母体染料，半波电势被阴极移动340–510 mV。生成了单电子还原形式和一些单电子氧化形式，并通过UV / vis / NIR和EPR光谱以及TD-DFT计算进行了研究。它们的光谱的那些的其他BODIPY染料的单电子还原或氧化形式以及相似度的丰富的结构EPR谱和克-值接近克Ë证实了有关前沿的MO的显性BODIPY字符。
京公网安备 11010802027423号