The ability of zirconium metal–organic frameworks (MOFs) to gelate under specific synthetic conditions opens up new opportunities in the preparation and shaping of hierarchically porous MOF monoliths, which could be directly implemented for catalytic and adsorptive applications.

Here we describe the synthesis and postsynthetic modification of the stable β-ketoenamine TpBD(NH 2 ) 2 covalent organic framework (COF), having primary amine groups integrated into the pore walls. For this purpose we initially synthesized the nitro version of this COF, TpBD(NO 2 ) 2 . Afterward, TpBD(NO 2 ) 2 was reduced to afford the desired framework having primary amine functionality. We demonstrate the accessibility of the primary amine groups and the robustness of the framework by a second modification step, the aminolysis of acetic anhydride, to obtain the corresponding amide form TpBD(NHCOCH 3 ) 2 . Taking advantage of the high stability of these frameworks under acidic conditions, we study the liquid-phase adsorption of lactic acid, revealing the strong impact of a pore wall modification on the adsorption performance.

The performance of modern chips is strongly related to the multi-layer interconnect structure that interfaces the semiconductor layer with the outside world. The resulting demand to continuously reduce the k-value of the dielectric in these interconnects creates multiple integration challenges and encourages the search for novel materials. Here we report a strategy for the integration of metal-organic frameworks (MOFs) as gap-filling low-k dielectrics in advanced on-chip interconnects. The method relies on the selective conversion of purpose-grown or native metal-oxide films on the metal interconnect lines into MOFs by exposure to organic linker vapor. The proposed strategy is validated for thin films of the zeolitic imidazolate frameworks ZIF-8 and ZIF-67, formed in 2-methylimidazole vapor from ALD ZnO and native CoO x , respectively. Both materials show a Young’s modulus and dielectric constant comparable to state-of-the-art porous organosilica dielectrics. Moreover, the fast nucleation and volume expansion accompanying the oxide-to-MOF conversion enable uniform growth and gap-filling of narrow trenches, as demonstrated for 45 nm half-pitch fork-fork capacitors.

Metal-organic frameworks (MOFs) enable the design of host-guest systems with specific properties.I nt his work, we showh ow the confinement of anthracene in aw ellchosen MOF host leads to reversible yellow-to-purple photoswitching of the fluorescence emission. This behavior has not been observed before for anthracene,e ither in pure form or adsorbed in other porous hosts.The photoresponse of the hostguest system is caused by the photodimerization of anthracene, which is greatly facilitated by the pore geometry,c onnectivity, and volume as well as the structural flexibility of the MOF host. The photoswitching behavior was used to fabricate photopatternable and erasable surfaces that, in combination with data encryption and decryption, hold promise in product authentication and secure communication applications.