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作 者:张璐[1] 曾涑源[2] 刘涛[3] 孙君善[1] 窦建民[2] 姜建壮[1]
机构地区:[1]北京科技大学化学与生物工程学院,功能分子与晶态材料科学与应用北京市重点实验室,北京100083 [2]聊城大学化学系,聊城252004 [3]大连理工大学,精细化工国家重点实验室,大连116012
出 处:《无机化学学报》2015年第9期1761-1773,共13页Chinese Journal of Inorganic Chemistry
基 金:国家自然科学基金(No.21290174);国家重点基础研究发展计划(973计划)(No.2013CB933402和No.2012CB224801)
摘 要:通过在铽的酞菁卟啉混杂三层的卟啉周边共价连接体积庞大的笼型倍半硅氧烷(POSS),得到了首个包含POSS的混杂三层Tb2(Pc)[T(OPOSS)4PP]2(1)[H2Pc=phthalocyanine;H2T(OPOSS)4PP=5,10,15,20-tetra{[[N-[heptakis(isobutyl)propoxy]phenyl]octasiloxane]}porphyrin]。为了对比研究,同时合成了类似的三层化合物Tb2(Pc)(TPP)2(2)(H2TPP=5,10,15,20-tetraphenyporphyrin)。尤其值得注意的是,在没有外加磁场的条件下,Tb2(Pc)[T(OPOSS)4PP]2(1)和Tb2(Pc)(TPP)2(2)分别表现出单分子磁体和非单分子磁体的性质,这充分说明了共价连接均匀分布的POSS基团有效地分离了磁性核心,从而改善了酞菁卟啉混杂三层的磁性。Bulky inorganic polyhedral oligomeric porphyrin periphery in mixed (phthalocyaninato) triple-decker complex Tb2(Pe)IT (0POSS)4PP]z (1) silsesquioxanes (POSS) moieties were introduced onto the (porphyrinato) terbium molecule, giving POSS-involved hybrid [H2Pc =phthalocyanine; HeT (OPOSS)4PP=5,10,15,20-tetra {[IN- [heptakis (isobutyl)propoxy]phenyl]octasiloxane]}porphyrin]. For corn- parative study, triple-decker analogue Tb2(Pc) (TPP)2 (2) (H2TPP=5,10,15,20-tetraphenyporphyrin) was also prepared and structurally characterized. In particular, Tb2(Pc)[T(OPOSS)4PP]2 (1) and Tb2(Pc)(TPP)2 (2) were revealed to display intrinsic single molecule magnet (SMM) and non-SMM (or field-induced) characteristic, respectively, at zero Oe (or a 3.00e ac field), clearly indicating the effect of the covalently linked, homogenously dispersed POSS moieties on effectively separating the magnetic cores and improving the magnetic property of triple-decker compounds. CCDC: 989974, 2.
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