The guest-dependent thermal response of the flexible MOF Zn(BDC)(DABCO)

The guest-dependent thermal response of the flexible MOF Zn 2 (BDC) 2 (DABCO) ( 1 ) has been studied. A series of temperature-dependent single crystallographic analyses revealed inherent structural thermal responses of 1 . The guest-free framework 1 exhibited interesting thermal responses including anisotropic thermal expansion (negative thermal expansion (NTE) along the a - and b -axes, positive thermal expansion (PTE) along the c -axis) and disorder-order phase transition. In addition, inclusion of guest molecules (DMF and benzene) brought distinct thermal responses to 1 from host-guest interactions. 1 ·4DMF showed altered thermal responses, presenting disorder-order phase transitions at a higher temperature and PTE along the a - and b -axes. Meanwhile, 1 ·3benzene displayed a quite different type of thermal response such as a hinge like motion (breathing) without a symmetry change. The flexible MOF, Zn 2 (BDC) 2 (DABCO) presents unusual guest-dependent structural responses upon temperature changes.