Two series of novel organic–inorganic hybrid carboxylated rare-earth-substituted monolacunary Dawson-type phosphotungstate monomers [Hdap]₄[RE(H₂O)(Hpic)₃][RE(Hpic)₂ (α₂-P₂W₁₇O₆₁)]·21H₂O [RE = Gd^III (1), Tb^III (2), Dy^III (3), Ho^III (4), Er^III (5), Tm^III (6), Yb^III (7), Y^III (8); Hpic = 2-picolinic acid, dap = 1,2-diaminopropane] and dimers [H₂dap]₈[RE₂(H₂ox)₂(ox)(α₂-P₂W₁₇O₆₁)₂]·25H₂O [RE = Ho^III (9), Er^III (10), Tm^III (11), Yb^III (12), Y^III (13); H₂ox = oxalic acid] have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, thermogravimetric measurements, and X-ray single-crystal diffraction. The monomeric polyoxoanion skeleton of isomorphic 1–8 is constructed from a monolacunary Dawson-type phosphotungstate implanted by a [RE1(Hpic)₂]³⁺ cation in the polar position and supported by the other [RE₂(H₂O)(Hpic)₃]³⁺ cation on the equatorial belt. Interestingly, two kinds of RE cations separately coordinate to two or three Hpic ligands in the form of N–C–C–O–RE containing five-membered ring fashion. The dimeric polyoxoanion backbone of isomorphic 9–13 is built by two mono-RE substituted Dawson-type phosphotungstate fragments [RE(H₂ox)(α₂-P₂W₁₇O₆₁)]^7– joined together by an ox^2– linker. The visible photoluminescence spectra of solid-state 2, 3, 5, and 10 and the NIR photoluminescence properties for solid-state 5, 10, 7, and 12 at ambient temperature have been carried out, which are mainly derived from the RE³⁺ f–f electron transitions. Magnetic susceptibility measurements and fitting results of 3 demonstrate that 3 is a single-molecule magnet.

中文翻译：

---

羧基配体官能化的两个稀土取代的道森型单体和二聚体磷钨酸盐家族

两个系列的新的有机-无机杂化的羧化稀土类-取代monolacunary道森-型磷钨单体[HDAP] ₄ [RE（H ₂ O）（HPIC）₃ ] [RE（HPIC）₂（α ₂ -P ₂ w ^ ₁₇ O ₆₁）]·21H ₂ O [RE = Gd ^III（1），Tb ^III（2），Dy ^III（3），Ho ^III（4），Er ^III（5），Tm ^III（6），Yb ^III（O7），Y ^III（8）；HPIC = 2-吡啶甲酸，DAP = 1,2-二氨基丙烷]和二聚物[H ₂ DAP] ₈ [RE ₂（H ₂ OX）₂（OX）（α ₂ -P ₂ w ^ ₁₇ ö ₆₁）₂ ]·25H ₂ O [RE = Ho ^III（9），Er ^III（10），Tm ^III（11），Yb ^III（12），Y ^III（13）；高₂ox =草酸]已通过水热合成，并通过元素分析，IR光谱，热重测量和X射线单晶衍射进行了表征。的同构的单体多氧阴离子骨架1 - 8是从由植入monolacunary道森-型磷钨[RE1（HPIC）构建₂ ] ³⁺阳离子的极性位置并支持其它[RE ₂（H ₂ O）（HPIC ）₃ ] ³⁺阳离子在赤道带上。有趣的是，两种RE阳离子分别以包含五元环形式的N–C–OC–O–RE的形式与两个或三个Hpic配体配位。同构的二聚体聚氧阴离子主链9 - 13由两个单RE取代道森-型磷钨片段[RE（H内置₂ OX）（α ₂ -P ₂ w ^ ₁₇ ö ₆₁）] ^7-由牛接合在一起^2-接头。的固态可见光光致发光光谱2，3，5，和10以及用于固态的NIR光致发光特性5，10，7，和12在环境温度下已进行了，其主要是从RE衍生³⁺f–f电子跃迁。3的磁化率测量和拟合结果表明3是单分子磁体。