(30e) A Combined Experimental-Simulation Design Approach to Multi-Porous Covalent Organic Frameworks (COFs)
In this talk, we will specifically demonstrate this computational-experimental design approach for the direct, bottom-up synthesis of a new tri-porous COF comprised of a combined imine and boronate ester backbone. New structural BBs, with geometry and orthogonal functionalities identified by coarse-grained simulations, have been synthesized and successfully assembled, under ambient to solvothermal conditions, into extended structures. Synthesis-structure relations correlating the extent of crystallinity of the resulting frameworks with solvents and catalysts used for solvothermal synthesis will be presented. Specifically, comparisons will be made between how acetic acid versus Lewis acids (e.g., metal triflate)2 can be exploited to selectively catalyze imine bond formation without affecting borane bond formation. Comprehensive characterization of the structure and stability of these materials will be presented, including insight into the tri-porous framework by a combination of N2, Ar, and CO2 physisorption and X-ray diffraction indexed on the basis of simulated diffraction patterns. Solid-state NMR, FTIR, CHN elemental analysis, and XPS reveal insight into the imine and boronate ester linkages, and SEM and TEM analyses have been used to investigate the morphology and porous architecture. On the basis of this example, the prospects of the computational-experimental design approach for the rational design of application-tailored COFs tailored will be discussed.