A direct anchoring of Anderson-type polyoxometalates in aqueous media with tripodal ligands especially containing the carboxyl group

Abstract

Polyoxometalate-based organic-inorganic hybrids were synthesized by direct modification of the parent Anderson cluster with both the traditional tripodal ligand, CH3C(CH2OH)3, and a novel one containing a carboxyl group, CH3C(CH2OH)2(COOH), which was inaccessible from the traditional self-assembly protocol.

The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”

“…the available functional groups that have been attached and the coupling reagent used. It is also possible to attach tris-ligands where one of the three hydroxyl groups has been exchanged with a carboxylic group [189]. The single-side decoration with tris-ligands breaks down the rather high symmetry in the parent Anderson-Evans cluster and the mixed enantiomers formed can be separated [102] in mixed organic solvents such as 60/40 DMF/MeCN (v/v) upon small additions of TBABr.…”

Single-Atom Mn Active Site in a Triol-Stabilized β-Anderson Manganohexamolybdate for Enhanced Catalytic Activity towards Adipic Acid Production

“…For the organoimidization functionalized POM derivatives, the aromatic segment was directly linked on the POM cluster through the Mo≡N bond, thus the conjugated electron of organic ligands obviously enriched the POM nanocluster through delocalization [30]. However, for the alkoxylation modification of the Anderson nanocluster, organic ligand electronic-driven effect was not obvious and can be ignored, as only slight electronic depletion that cause hypsochromic shift was observed, as we investigated before [38]. Hence, the triol ligand just plays an important role in stabilizing β-{[H 3 NC(CH 2 O) 3 ] 2 MnMo 6 O 18 } as the specific butterfly-shaped topology according to the DFT calculations we reported before [37].…”

“…In addition, POMs could not only serve as co-catalysts but could stabilize the active metal sites and regulate the electronic structure of catalysts to give rise to the enhancement of catalytic activities [32][33][34][35]. Over the years, our group has dedicated substantial efforts on the development of organically functionalized Anderson-type POMs [30,[36][37][38][39][40][41][42][43]. Thus, we predicted that the Anderson-type POMs with manganese as the active metal site might catalyze the green oxidation of cyclohexanone, cyclohexanol, and KA oil to AA with high reactivity.…”

Recent advances in controllable alkoxylation chemistry of Anderson-type polyoxometalates from synthetic strategies perspective

“…杨国昱课题组 [23] 则利用 Cnnizzaro反应合成了远端带有配位活性吡啶环刚性 新 型三羟甲基 类有机配体 C 5 H 4 NC(CH 2 O) 3 [23,24] . 总之运用直接修饰法, 以烷氧 3 [13,15] .…”

“…在本课题组 [10] 提出直接法对多酸进行烷氧化修 饰之前, 多酸的烷氧化修饰主要是采用Haseknop [8,9] 提出的传统重构法对多酸修饰的基础之上开展的. [11] 、 双侧不对称有机烷氧化修饰 [12] 的合成方法, 并拓宽 了用于Anderson型杂多酸有机共价修饰的烷氧有机 配体的选择范围 [13] , 成功实现杂多酸骨架上μ 2 -O原 子的活化 [14] , 更重要的是, 研究了对杂多酸的烷氧 化修饰模式及其异构体 [15] 制备方法. 此外, 还以平 面构型Anderson型杂多酸α异构体为前驱体制备了具 有蝴蝶拓扑构型的同类型杂多酸烷氧衍生物的β异构 体 [16,17] .…”