Positive and Negative Two-Dimensional Thermal Expansion via Relaxation of Node Distortions

The ability to tune physical properties is attractive for the development of new materials for myriad applications. Understanding and controlling the structural dynamics in complicated network structures like coordination polymers (CPs) is particularly challenging. We report a series of two-dimensional CPs [Mn(salen)]₂[M(CN)₄]· xH₂O (M = Pt (1), PtI₂ (2), and MnN (3)) incorporating zigzag cyano-network layers that display composition-dependent anisotropic thermal expansion properties. Variable-temperature single-crystal X-ray structural analyses demonstrated that the thermal expansion behavior is caused by double structural distortions involving [Mn(salen)]⁺ units incorporated into the zigzag layers. Thermal relaxations produce structural transformations resulting in positive thermal expansion for 2·H₂O and negative thermal expansion for 3. In the case of 1·H₂O, the relaxation does not occur and zero thermal expansion results in the plane between 200 to 380 K. The present study proposes a new strategy based on structural distortions in coordination networks to control thermal responsivities of frameworks.