By reacting a 3,6-ditriazolyl-2,5-dihydroxybenzoquinone(H_(2)trz_(2)An)anilato linker with Ln^(Ⅲ) ions(Ln^(Ⅲ)=Dy,Tb,Ho),two different series of polymorphs,formulated as[Ln_(2)(trz_(2)An)_(3)(H_(2)O)_(4)]n·10H_(...By reacting a 3,6-ditriazolyl-2,5-dihydroxybenzoquinone(H_(2)trz_(2)An)anilato linker with Ln^(Ⅲ) ions(Ln^(Ⅲ)=Dy,Tb,Ho),two different series of polymorphs,formulated as[Ln_(2)(trz_(2)An)_(3)(H_(2)O)_(4)]n·10H_(2)O(Dy^(Ⅲ),1a;Tb^(Ⅲ),2a,Ho^(Ⅲ),3a)and[Ln_(2)(trz_(2)An)_(3)(H_(2)O)_(4)]n·7H_(2)O(Dy^(Ⅲ),1b,Tb^(Ⅲ),2b,Ho^(Ⅲ),3b)have been obtained.In these series the two Dy^(Ⅲ)-coordination networks(1a and 1b)and the Tb^(Ⅲ)-coordination polymer(2b)show a Single Ion Magnet(SIM)behavior.1–3a MOFs show reversible structural flexibility upon removal of a coordinated water molecule from a distorted hexagonal 2D framework to a distorted 3,6-brickwall rectangular 3D structure in[Ln_(2)(trz_(2)An)_(3)(H_(2)O)_(2)]n·2H_(2)O(Dy^(Ⅲ),1a_des;Tb^(Ⅲ),2a_des,Ho^(Ⅲ),3a_des)involving shrinkage/expansion of the hexagonal–rectangular networks.Noteworthy,2b represents the first example of a Tb^(Ⅲ)–anilate-based coordination polymer showing SIM behaviour to date and the best SIM properties within the polymorphs.Theoretical investigation via ab initio CASSCF calculations supports this behavior,since 2b shows less mixing between the mJ states of the ground state among all the studied complexes.展开更多
基金support from the EU(ERC Advanced Grant MOL-2D 788222)the Spanish MCIN(Grants PID2020-117264GB-I00 and PID2020-117152RB-I00 funded by MCIN/AEI/10.13039/501100011033 and Unidad de Excelencia María de Maeztu CEX2019-000919-M)and the Generalitat Valenciana(PROMETEO program),is acknowledged+3 种基金supported by MCIN with funding from the European Union NextGenerationEU(PRTR-C17.I1)and by Generalitat Valenciana.JJB and SD would like to thank EU(Grant No.2D-SMARTiES ERC-StG-101042680 and Marie Curie Fellowship SpinPhononHyb2D 101107713)the Plan Gent of Excellence of the Generalitat Valenciana(Grant No.CDEIGENT/2019/022)for the fundingfunded in Italy by Fondazione di Sardegna,Convenzione Triennale tra la Fondazione di Sardegna e gli Atenei Sardi,Regione Sardegna,L.R.7/2007 annualità2022,project VOC_3D“3D printed optical VOC sensors for indoor air quality evaluation”CUP F73C23001590007Alejandra Soriano-Portillo for PXRD measurements and J.M.Martínez-Agudo and G.Agustífor magnetic measurements.
文摘By reacting a 3,6-ditriazolyl-2,5-dihydroxybenzoquinone(H_(2)trz_(2)An)anilato linker with Ln^(Ⅲ) ions(Ln^(Ⅲ)=Dy,Tb,Ho),two different series of polymorphs,formulated as[Ln_(2)(trz_(2)An)_(3)(H_(2)O)_(4)]n·10H_(2)O(Dy^(Ⅲ),1a;Tb^(Ⅲ),2a,Ho^(Ⅲ),3a)and[Ln_(2)(trz_(2)An)_(3)(H_(2)O)_(4)]n·7H_(2)O(Dy^(Ⅲ),1b,Tb^(Ⅲ),2b,Ho^(Ⅲ),3b)have been obtained.In these series the two Dy^(Ⅲ)-coordination networks(1a and 1b)and the Tb^(Ⅲ)-coordination polymer(2b)show a Single Ion Magnet(SIM)behavior.1–3a MOFs show reversible structural flexibility upon removal of a coordinated water molecule from a distorted hexagonal 2D framework to a distorted 3,6-brickwall rectangular 3D structure in[Ln_(2)(trz_(2)An)_(3)(H_(2)O)_(2)]n·2H_(2)O(Dy^(Ⅲ),1a_des;Tb^(Ⅲ),2a_des,Ho^(Ⅲ),3a_des)involving shrinkage/expansion of the hexagonal–rectangular networks.Noteworthy,2b represents the first example of a Tb^(Ⅲ)–anilate-based coordination polymer showing SIM behaviour to date and the best SIM properties within the polymorphs.Theoretical investigation via ab initio CASSCF calculations supports this behavior,since 2b shows less mixing between the mJ states of the ground state among all the studied complexes.
