Bazi Marco, Bracciotti Edoardo, Fioravanti Lorenzo, Marchetti Fabio, Rancan Marzio, Armelao Lidia, Samaritani Simona, Labella Luca
Dipartimento di Chimica e Chimica Industriale and CIRCC, Università di Pisa, via Giuseppe Moruzzi 13, I-56124 Pisa, Italy.
CNR ICMATE and INSTM, c/o Dipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, I-35131 Padova, Italy.
Inorg Chem. 2024 Apr 29;63(17):7678-7691. doi: 10.1021/acs.inorgchem.3c04532. Epub 2024 Apr 16.
Rare-earth tris-diketonato [RE(dike)pyterpy] metalloligands can be prepared reacting at room temperature [RE(dike)dme] (dme = 1,2-dimethoxyethane; dike = tta with Htta = 2-thenoyltrifluoroacetone and RE = La, ; Y, ; Eu, ; Dy, ; or dike = hfac with Hhfac hexafluoroacetylacetone, and RE = Eu, ; Tb, ; Yb ) with 4'-(4‴-pyridil)-2,2':6',2″-terpyridine (pyterpy). The molecular structures of , , , and have been studied through single-crystal X-ray diffraction showing mononuclear neutral complexes with the rare-earth ion in coordination number nine and with a muffin-like coordination geometry. [RE(tta)pyterpy] promptly reacts with [M(tta)dme] with formation of [Mpyterpy][RE(tta)] (M = Zn, RE = Y, ; M = Co, RE = Dy, ). Consistently, [Zn(hfac)dme] reacts at room temperature with 2 equiv of pyterpy yielding [Znpyterpy][hfac] that easily can be transformed by reaction with 2 equiv of [Eu(hfac)] in [Znpyterpy][Eu(hfac)] that has been structurally characterized. Finally, , , , , and metalloligands react at room temperature in few minutes with [PtCl(μ-Cl)PPh] yielding the heterometallic molecular complexes [RE(dike)pyterpyPtClPPh] (dike = tta, RE = La, ; Y, ; Eu; ; dike = hfac, RE = Eu, ; Yb, ).
稀土三二酮基[RE(dike)pyterpy]金属配体可通过在室温下使[RE(dike)dme]（dme = 1,2 - 二甲氧基乙烷；dike = tta，其中Htta = 2 - 噻吩甲酰三氟丙酮，RE = La、Y、Eu、Dy；或dike = hfac，其中Hhfac = 六氟乙酰丙酮，RE = Eu、Tb、Yb）与4'-(4‴-吡啶基)-2,2':6',2″-三联吡啶（pyterpy）反应来制备。通过单晶X射线衍射研究了[RE(tta)pyterpy]、[RE(hfac)pyterpy]（RE = Eu、Tb、Yb）的分子结构，结果表明它们是单核中性配合物，稀土离子的配位数为9，具有松饼状的配位几何结构。[RE(tta)pyterpy]能迅速与[M(tta)dme]反应生成[Mpyterpy][RE(tta)]（M = Zn，RE = Y；M = Co，RE = Dy）。同样，[Zn(hfac)dme]在室温下与2当量的pyterpy反应生成[Znpyterpy][hfac]，该产物通过与2当量的[Eu(hfac)]反应可轻松转化为已进行结构表征的[Znpyterpy][Eu(hfac)]。最后，[RE(tta)pyterpy]、[RE(hfac)pyterpy]（RE = Eu、Tb、Yb）金属配体在室温下几分钟内就能与[PtCl(μ-Cl)PPh₃]反应生成异金属分子配合物[RE(dike)pyterpyPtClPPh₃]（dike = tta，RE = La、Y、Eu；dike = hfac，RE = Eu、Yb）。
