The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets.In this context,the use of expanded porphyrinoids remains elusive since their coordin...The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets.In this context,the use of expanded porphyrinoids remains elusive since their coordination chemistry is challenging to control.Herein,taking inspiration from on-surface chemistry,we explored the coordination of Dy^(3+)to a six-membered porphyrinoid,namely,the hemihexaphyrazine H3Hhp.Remarkably,we observed the selective formation of a mono-nuclear off-centered,out-of-plane H_(2)Hhp-Dy^(3+)complex when performing the complexation under reductive conditions.During this reaction,the oxidation state of the macrocycle did not change.Employing X-ray diffraction analysis,we found that the coordination number of Dy in this complex was 8.The macrocycle cocrystallized with decamethylcobaltocene(Cp_(2)^(*)Co)molecules,giving rise to a wellordered solid-state packing,governed byπ-πinteractions.As a result of this organization,a small magnetic coupling between the neighboring molecules was observed.All in all,this work provides key insights into the coordination of magnetically active metals with expanded porphyrinoids,thus motivating the development of advanced spintronic devices.展开更多
基金financial support from the Russian Science Foundation (project N 21-13-00221)for the synthesis and studies of optical and magnetic properties of 1supported by the Ministry of Science and Higher Education of the Russian Federation (Registration number 124013100858-3)+2 种基金E.N.I.and M.K.I.acknowledge Grant from the Ministry of Science and Higher Education of the Russian Federation (no.075-15-2021-579)for synthesis of H3Hhp and preliminary DFT calculationssupport from the Spanish MCIN/AEI/10.13039/501100011033 (PID2020-116490GB-I00,TED2021-131255B-C43)the Comunidad de Madrid,and the Spanish State through the Recovery,Transformation and Resilience Plan[“Materiales Disruptivos Bidimensionales (2D)” (MAD2D-CM) (UAM1)-MRR Materiales Avanzados],and the European Union through the Next Generation EU funds.Instituto madrileno de estudios avanzados Nanociencia acknowledges support from the“Severo Ochoa”Programme for Centres of Excellence in R&D (Ministerio de asuntos economicos y transformacion digital,Grant SEV2016-0686).
文摘The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets.In this context,the use of expanded porphyrinoids remains elusive since their coordination chemistry is challenging to control.Herein,taking inspiration from on-surface chemistry,we explored the coordination of Dy^(3+)to a six-membered porphyrinoid,namely,the hemihexaphyrazine H3Hhp.Remarkably,we observed the selective formation of a mono-nuclear off-centered,out-of-plane H_(2)Hhp-Dy^(3+)complex when performing the complexation under reductive conditions.During this reaction,the oxidation state of the macrocycle did not change.Employing X-ray diffraction analysis,we found that the coordination number of Dy in this complex was 8.The macrocycle cocrystallized with decamethylcobaltocene(Cp_(2)^(*)Co)molecules,giving rise to a wellordered solid-state packing,governed byπ-πinteractions.As a result of this organization,a small magnetic coupling between the neighboring molecules was observed.All in all,this work provides key insights into the coordination of magnetically active metals with expanded porphyrinoids,thus motivating the development of advanced spintronic devices.
