{P2V3W15}-Polyoxometalates Functionalized with Phthalocyaninato Y and Yb Moieties.
{P2V3W15}-Polyoxometalates Functionalized with Phthalocyaninato Y and Yb Moieties.
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DOI：
10.1021/acs.inorgchem.0c02257
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发表时间：
2020-11
影响因子：
4.6
通讯作者：
Ricarda Pütt;P. Kozłowski;Irina Werner;J. Griebel;Sebastian Schmitz;J. Warneke;K. Monakhov
中科院分区：
文献类型：
--
作者：
Ricarda Pütt;P. Kozłowski;Irina Werner;J. Griebel;Sebastian Schmitz;J. Warneke;K. Monakhov
三（烷氧基）吡啶增强的well - dawson多金属氧酸盐（nBu4N）6[WD-Py] （WD = P2V3W15O59(OCH2)3C, Py = C5H4N）与酞菁基金属基团（MPc，其中M = Y或Yb， Pc = C32H16N8）功能化得到（nBu4N）4[HWD-Py(MPc)]化合物。采用高分辨率质谱法对混合装配体进行检测和鉴定。磁性研究揭示了M = Yb（单体，单离子顺磁性）和M = Y（含二聚体，自由基特征）之间的本质差异。电子顺磁共振光谱、SQUID磁强计和磁化学计算的结果表明，分子内电荷从MPc片段转移到多金属氧酸盐，分子间电荷从一个分子的MPc片段转移到另一个分子的多金属氧酸盐单元。这些具有VIV离子的化合物代表了过渡金属/镧系配合物- pom杂化化合物在电子供体和受体中心之间具有非光致电荷转移的独特例子。
A tris(alkoxo)pyridine-augmented Wells-Dawson polyoxometalate (nBu4N)6[WD-Py] (WD = P2V3W15O59(OCH2)3C, Py = C5H4N) was functionalized with phthalocyaninato metal moieties (MPc where M = Y or Yb and Pc = C32H16N8) to afford (nBu4N)4[HWD-Py(MPc)] compounds. High-resolution mass spectrometry was used to detect and identify the hybrid assembly. The magnetism studies reveal substantial differences between M = Yb (monomeric, single-ion paramagnetism) and M = Y (containing dimers, radical character). The results of electronic paramagnetic resonance spectroscopy, SQUID magnetometry, and magnetochemical calculations indicate the presence of intramolecular charge transfer from the MPc moiety to the polyoxometalate and of intermolecular charge transfer from the MPc moiety of one molecule to the polyoxometalate unit of another molecule. These compounds with identified VIV ions represent unique examples of transition-metal/lanthanide complex-POM hybrid compounds with nonphotoinduced charge transfer between electron donor and acceptor centers.