Magnetically Isolated CuIIGdIII Pairs in the Series [Cu(acacen)Gd(pta)3], [Cu(acacen)Gd(hfa)3], [Cu(salen)Gd(pta)3], and [Cu(salen)Gd(hfa)3<

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• 作者：M. Ryazanov ; V. Nikiforov ; F. Lloret ; M. Julve ; N. Kuzmina ; and A. Gleizes
• 刊名：Inorganic Chemistry
• 出版年：2002
• 出版时间：April 8, 2002
• 年：2002
• 卷：41
• 期：7
• 页码：1816 - 1823
• 全文大小：130K
• 年卷期：v.41,no.7(April 8, 2002)
• ISSN：1520-510X

文摘

[Cu(salen)Gd(pta)₃] (1), [Cu(acacen)Gd(pta)₃] (2), and [Cu(acacen)Gd(hfa)₃] (3) are three heterobimetallic[Cu^IIGd^III] complexes of general formula [Cu(SB)Gd(mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-dik)₃], in which a N,N',O,O' Schiff base (SB) ligand [acacen= N,N'-ethylenebis(acetylacetoniminate(-)), salen = N,N'-ethylenebis(salicylideneiminate(-))] tetracoordinates Cu^IIand chelates Gd^III as a tris(mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-diketonate) complex [hfa = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate(-); pta = 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dionate(-)]. They crystallize as a triclinic structure (space group Pmages/entities/onemacr.gif">). The cellparameters are a = 9.8616(10) Å, b = 12.1976(13) Å, c = 18.4187(22) Å, mages/gifchars/alpha.gif" BORDER=0> = 90.671(14)mages/entities/deg.gif">, mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 100.588(13)mages/entities/deg.gif">,mages/gifchars/gamma.gif" BORDER=0 > = 103.684(12)mages/entities/deg.gif">, V = 2113 ų, and Z = 2 for 1; a = 9.7560(11) Å, b = 12.2924(13) Å, c = 18.9368(22) Å,mages/gifchars/alpha.gif" BORDER=0> = 88.449(14)mages/entities/deg.gif">, mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 87.269(14)mages/entities/deg.gif">, mages/gifchars/gamma.gif" BORDER=0 > = 67.629(12)mages/entities/deg.gif">, V = 2098 ų, and Z = 2 for 2; and a = 12.5726(15) Å,b = 15.5985(18) Å, c = 18.3724(21) Å, mages/gifchars/alpha.gif" BORDER=0> = 85.963(13)mages/entities/deg.gif">, mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle"> = 85.411(14)mages/entities/deg.gif">, mages/gifchars/gamma.gif" BORDER=0 > = 80.766(14)mages/entities/deg.gif">, V = 3539 ų, andZ = 4 for 3. The Cu(O,O')Gd bridging cores show folding angles about O,O' in the range 139mages/entities/deg.gif">-147mages/entities/deg.gif"> andintramolecular Cu···Gd distances of about 3.3 Å. In the solid state, the molecules form centrosymmetric pseudodimers[Cu(SB)Gd(mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-dik)₃]₂, through the overlap of the Cu(SB) entities. Resulting intradimer Cu···Cu distances are 5.941(1) Å for 1, 4.831(1) Å for 2, and 4.511(1) and 3.868(1) Å for 3 which comprises two symmetrically independentdimers. The temperature dependence of complexes 1-3 was investigated in the range 1.8-300 K and revealedweak ferromagnetic interactions. Results are discussed in light of the structural features and of availablemagnetostructural data for other heterobimetallic [Cu^IIGd^III] complexes, including [Cu(salen)Gd(hfa)₃] (4) (Ramade,I.; Kahn, O.; Jeannin, Y.; Robert, F. Inorg. Chem. 1997, 36, 930-936).