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

Inorganic Chemistry
Michał MagottDawid Pinkowicz

Abstract

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 dppipH22+ 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-te...Continue Reading

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Methods Mentioned

BETA
X-ray
differential scanning calorimetry
single-crystal diffraction
circular dichroism

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