Multifunctionality and Crystal Dynamics of a Highly Stable, Porous Metal−Organic Framework [Zn₄O(NTB)₂]

A porous metal−organic framework [Zn4O(NTB)2]·3DEF·EtOH (1), in which (3,6)-connected nets are doubly interpenetrated to generate curved three-dimensional channels, has been prepared. Framework 1 exhibits high permanent porosity (Langmuir surface area, 1121 m2/g; pore volume, 0.51 cm3/cm3), high thermal stability (up to 430 °C), high hydrogen adsorption capacity (1.9 wt % at 77 K and 1 atm), selective organic guest binding ability (Kf : MeOH > pyridine > benzene > dodecane), and guest-dependent blue luminescence (λmax depending on guest identity). Most interestingly, the framework sustains single crystallinity even at 400 °C and 10-5 Torr, and the framework components undergo reversible dynamics, mainly rotational motion, in response to removal and rebinding of the guest molecules.