Selective Capture of CWAs and Containment of Their Neutralization Byproducts by Porous Frameworks Presenting Self-Amplifying and Self-Regulating Reactivities

We have designed and synthesized highly porous COFs and MOFs as functional architectures that are capable of capturing volatile TICs. In parallel, we have explored novel crystalline porous materials that have reactive sites and functionalities, which can be controlled by an external stimulus. We demonstrated that reticular chemistry facilitates the design and synthesis of new robust COFs, as well as isoreticular covalent functionalization and metallation. In addition, a MOF with self-contained photo-active switches was prepared. As stimuli-responsive functional molecules that can release multiple copies of nucleophilic agents to combat electrophilic CWAs, we have developed linear/branched oligoether/esters. Upon cleavage of a Si–O bond, fast and repetitive QM rearrangement occur along the molecular backbone to release phenoxide derivatives that detoxify OP agent simluant. The progress of such reaction could be visually monitored by a large enhancement in the fluorescence intensity, which allows for detection and detoxification achieved by a single integrated molecular system. These functional modules could be grafted onto chemically modified inorganic surfaces. Shape-persistent conducting polymers were also prepared from borasiloxane cage molecules. The light-absorbing properties and electrical conductivities of these materials change in a reversible fashion upon exposure to volatile TICs. (a) Papers published in peer-reviewed journals (N/A for none) Enter List of papers submitted or published that acknowledge ARO support from the start of the project to the date of this printing. List the papers, including journal references, in the following categories: