Tetrakis-Cyanoacetylides as Building Blocks for a Second Generation of Spin-Switchable Hofmann-type Networks with Enhanced Porosity.

The combination of spin crossover (SCO) with guest incorporation properties has attracted the interest of researchers in the last couple of decades and has led to the design of numerous SCO porous coordination polymers (SCO-PCPs). The most famous class of SCO-PCPs is the Hofmann-type network, which is a very promising material for (chemo)sensing applications. Different strategies have been carried out to expand the classic structure {Fe(pz)[M II (CN) 4 ]} (M = Ni, Pd, Pt) to get larger cavities, but the resulting compounds often showed a poor magnetic behavior. In this work, we present wide-mesh-size spin-switching Hofmann-type networks based on tetrakis-cyanoacetylides synthesized with a newly developed method, resulting in compounds with the general formula {Fe(pz)[M(C 3 N) 4 ]} (M=Ni, Pd, Pt). The compounds were characterized in their structural, magnetic, and spectroscopic properties. They present 5-fold larger cavities and a drastic increase in porosity. The desired hysteretic and guest-dependent spin-crossover behavior is retained, and in situ chemo-switching of the spin state and the memory effect are also observed.