Heterotrimetallic Cyanide-Bridged 3d-4d-5d Frameworks Based on a Photomagnetic Secondary Building Unit

• Published in: Inorganic chemistry Vol. 59; no. 13; pp. 8925 - 8934
• Main Authors: Magott, Michał, Sarewicz, Marcin, Buda, Szymon, Pinkowicz, Dawid
• Format: Journal Article
• Language: English
• Published: American Chemical Society 06-07-2020
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.0c00737

The rational design of coordination frameworks combining more than two different metal ions using a self-assembly approach is challenging because it rarely offers sufficient control over the building blocks at the actual self-assembly stage. In this work, we present a successful two-step strategy toward heterotrimetallic coordination frameworks by employing a new bimetallic [(NC)7MoIV-CN-PtIV(NH3)4-NC-MoIV(CN)7]4– secondary building unit (SBU). This anionic moiety has been isolated and characterized as a simple salt with an organic dppipH2 2+ cation (dppipH2)2[(NC)7MoIV-CN-PtIV(NH3)4-NC-MoIV(CN)7]·15H2O (1) (dppip = 1,4-di­(4-pyridinyl)­piperazine). The salt presents a second-order phase transition related to cation conformational change around 250 K and a photomagnetic effect after irradiation with 450 nm light at 10 K. When combined with aqueous solutions of MnII or CuII complexes, it forms either a one-dimensional chain [MnII(dpop)]­[MnII(dpop)­(H2O)]­[(NC)7MoIV-CN-PtIV(NH3)4-NC-MoIV(CN)7]·36H2O (2) (dpop = 2,13-dimethyl-3,6,9,12,18-penta­aza­bicyclo-[12.3.1]­octa­deca-1(18),2,12,14,16-penta­ene) or a photomagnetic two-dimensional honeycomb network [CuII(cyclam)]2[(NC)7MoIV-CN-PtIV(NH3)4-NC-MoIV(CN)7]·40.89H2O (3) (cyclam = 1,4,8,11-tetra­aza­cyclo­tetra­decane), both characterized by very large cavities in their structure filled with solvent molecules. Both 2 and 3 incorporate three different transition-metal ions and constitute a new family of 3d-4d-5d coordination frameworks. Moreover, compound 3 inherits the photomagnetic properties of the MoPtMo SBU.