Expanded Porphyrin Exhibiting Off-Centered Out-of-Plane Coordination to Dysprosium  

作　　者：Dmitry I.Nazarov Jorge Labella Alexey V.Kuzmin Maxim A.Faraonov Evgenii N.Ivanov Salavat S.Khasanov Tomas Torres Mikhail K.Islyaikin Dmitri V.Konarev 

机构地区：[1]Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry RAS,142432 Chernogolovka [2]Department of Organic Chemistry,Universidad Autonoma de Madrid,28049 Madrid [3]Institute of Solid-State Physics RAS,142432 Chernogolovka [4]Research Institute of Macroheterocycles,Ivanovo State University of Chemistry and Technology,15300 Ivanovo [5]G.A.Krestov Institute of Solution Chemistry of the Russian Academy of Sciences,153045 Ivanovo [6]Institute for Advanced Research in Chemical Sciences,Universidad Autonoma de Madrid,28049 Madrid [7]IMDEA-Nanociencia,28049 Madrid

出　　处：《CCS Chemistry》2024年第7期1731-1738,共8页中国化学会会刊（英文）

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 1;supported by the Ministry of Science and Higher Education of the Russian Federation (Registration number 124013100858-3);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 calculations;support 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).

摘　　要：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.

关 键 词：PORPHYRINS DYSPROSIUM MACROCYCLE coordination chemistry MAGNETISM 

分 类 号：O62[理学—有机化学]