Search NASA⌕ Search

Engineering topics

Rupar, Paul A.

Publications and source records attributed to Rupar, Paul A..

5 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Detection of the BICT State in a Borafluorene with High Stokes Shift Fluorescence

Four-coordinate aryl borafluorenes with boron–oxygen and boron–nitrogen dative bonds can exhibit very large fluorescence Stokes shifts. The large Stokes shifts are hypothesized to arise from cleavage of the boron-donor dative bond in the excited state, via a mechanism called bond-cleavage-induced intramolecular charge transfer (BICT). The primary goal of this current investigation is to directly observe the BICT state by performing transient absorption spectroscopy (TAS) on four-coordinate borafluorenes, which have improved optical stability. A novel four-coordinate aryl borafluorene was synthesized which features a dative B–O bond and two tert-butyl moieties on the aryl ring. TAS of the new borafluorene is consistent with the existence of a single, three-coordinate species in the excited state, as predicted by the BICT hypothesis. In conclusion, the TAS data is supported by fluorescence lifetime measurements and DFT calculations.

Absorption↗
DOE OSTI2022

The Anionic Polymerization of a tert-Butyl-Carboxylate-Activated Aziridine

N-Sulfonyl-activated aziridines are known to undergo anionic-ring-opening polymerizations (AROP) to form polysulfonyllaziridines. However, the post-polymerization deprotection of the sulfonyl groups from polysulfonyllaziridines remains challenging. In this report, the polymerization of tert-butyl aziridine-1-carboxylate (BocAz) is reported. BocAz has an electron-withdrawing tert-butyloxycarbonyl (BOC) group on the aziridine nitrogen. The BOC group activates the aziridine for AROP and allows the synthesis of low-molecular-weight poly(BocAz) chains. A 13C NMR spectroscopic analysis of poly(BocAz) suggested that the polymer is linear. The attainable molecular weight of poly(BocAz) is limited by the poor solubility of poly(BocAz) in AROP-compatible solvents. The deprotection of poly(BocAz) using trifluoroacetic acid (TFA) cleanly produces linear polyethyleneimine. Overall, these results suggest that carbonyl groups, such as BOC, can play a larger role in the in the activation of aziridines in anionic polymerization and in the synthesis of polyimines.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Polymerizations of 2-(Trimethylsilyl)ethanesulfonyl-activated aziridines

A novel N-sulfonyl aziridine, N-((2-(trimethylsilyl)ethyl)sulfonyl)-2-methyl-aziridine (SES-MeAz) was synthesized, and its controlled anionic ring-opening polymerization to form poly(SES-MeAz) studied. The desulfonylation of poly(SES-MeAz)s can be achieved under mild conditions, with tetrabutylammonium fluoride (TBAF) to form polypropylene imine (PPI), although purification of the PPI was not completely successful. The block copolymer p(pTs-MeAz)-b-p(SES-MeAz), (pTs-MeAz = N-para-tosyl-2-methyl-aziridine) was prepared by a sequential polymerization. The desulfonylation of the block copolymer is the first example of the selective removal of a sulfonyl protecting group from a poly(sulfonylazirdine) block copolymer and this is the first formation of a polysufonylaziridine-block-polypropylene imine copolymer. Three-armed star-shaped poly(SES-MeAz)s were also successfully synthesized and exhibited improved solubility compared with linear poly(SES-MeAz)s.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Composite Correlated Molecular Orbital Theory Calculations of Ring Strain for Use in Predicting Polymerization Reactions

Strained ring systems play an important role in synthesis and can be characterized by the ring strain energy (RSE). The RSE of 3, 4, 5, and 6 membered saturated and unsaturated ring systems containing N, O, P, and S heteroatoms and H, F, SiMe 3 , and SO 2 Me substituents were calculated at the G3(MP2) composite correlated molecular orbital theory level using up to 5 models to predict the RSE. Generally, the RSE decreased as ring size increased with a substantial decrease from 4 to 5 membered rings. Replacement of a ring CH 2 with P or S reduced the RSE, consistent with less angle strain. The RSE for unsaturated systems were generally greater than for saturated systems due to increased angle strain. No general trends were found with respect to substituent effects. In conclusion, the RSE values suggest that 3-pyrroline and 2-pyrroline and their derivatives may be able to support ring opening metathesis polymerization and warrant further study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗