Characterizing Metal Coordination Environments in Porous Organic Polymers: A Joint Density Functional Theory and Experimental Infrared Spectroscopy Study

Abstract

Very POP right now! DFT computational analysis on the structural, energetic, and IR spectroscopic characteristics of a porous organic polymer support, [Ta(NMe2 )5 ] as a molecular precursor, and the catalytic material synthesized from these two components are presented and analyzed against recorded IR spectra of these systems. The analysis leads to unambiguous identification of the atomic structure of the POP-supported Ta-amide reaction center synthesized in the experiment.

Nondispersive Infrared Gas Analyzer for Partial Pressure Measurements of a Tantalum Alkylamide During Vapor Deposition Processes

“…In Fig. 1, The PDMAT and DMA spectra both exhibit relatively intense features in the fingerprint region below ≈1500 cm −1 and C–H stretching region from ≈2700 cm −1 to ≈3100 cm −1 , in agreement with previous reports for PDMAT 27–29 and DMA. 30–32 In both spectral regions, the molar absorptivity of PDMAT features tends to be larger than those of DMA.…”

“…Despite prolonged pumping on the PDMAT ampoule prior to each measurement, the DMA feature was always observed under the conditions employed in this work. The PDMAT feature observed at &946 cm À1 , attributed to the NC 2 symmetric stretching mode 27 or this mode coupled with the Ta-N stretching mode, 28 is intense and, therefore this feature was selected to monitor PDMAT, despite the potential for a weak interference between DMA and PDMAT. A filter with a center wavelength of &10.56 lm (947 cm À1 ), a FWHM of &0.24 lm, and a peak transmission of &86 % was used to isolate this feature.…”

“…[20][21][22][23][24][25][26] Of these demonstrated NDIR gas analyzers, a number operate based on isolating absorption modes in the C-H stretching spectral region. 21,25,26 Since both PDMAT and DMA absorb in this spectral region, [27][28][29][30][31][32] the potential for strong spectral interference between the two species is high in this region, complicating data analysis. To reduce the potential for interference between a metal alkylamide and the corresponding amine decomposition product, NDIR gas analyzers designed to monitor both species can be based on isolating absorption modes in the fingerprint spectral region.…”

Nanoporous Polymers: Bridging the Gap between Molecular and Solid Catalysts?

“…The opportunity for loading them post‐synthetically with different metal species such as magnesium, copper, and manganese was proven for a porous polymer containing a catechol derivative as the co‐monomer in the cyclotrimerization of ethynyl‐functionalized building blocks (Scheme ) 70. Recently, a combined density functional theory and spectroscopic study provided insight into the metal coordination environment within the nanoporous catechol‐containing polymers 71. Catalytic activity was shown for a microporous polyisocyanurate that was synthesized from bifunctional isocyanate linkers by a cyclotrimerization reaction catalyzed by a NHC (Scheme ) 18.…”