Hybrid inorganic-organic molecular materials hold great potential for electronic devices such as field-effect transistors and non-volatile memory devices. The increasing interest in these multifunctional materials stems from their modular synthetic procedures and the judicious choice of functional building units with pre-designed properties. The crystalline nature of these molecular materials also offers ideal platforms for the study of structure-property relationships which can serve as guidelines in the design of materials with improved properties. A facile modular synthetic approach has been developed by using Co(II) spin-crossover (SCO) units and pre-formed TCNQ radical precursors. One of the key designing strategies involves the direct incorporation of partially charged radicals for better conductivity instead of the previously reported galvanostatic oxidation and comproportionation methods. An anomalous electrical conducting behavior has been observed in [Co(terpy)2](TCNQ)3 CH3CN, which is composed of alternating semiconducting and spin-crossover layers. An unprecedented cross-stacking pattern of TCNQ radical triads is present in the structure. The electronic and steric properties of the SCO units are also modulated by expanding the organic ligands of the SCO units, which has induced interesting magnetic properties. These Co(II) SCO units have also been successfully incorporated into extended structures such as 1-D chains and 3-D frameworks which retains the original SCO properties.

Functional molecular materials based on cobalt(II) spin-crossover building units

251st National Meeting (2016)

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