Cryogenic ion vibrational predissociation (CIVP) spectroscopy of a gas-phase molecular torsion balance to probe London dispersion forces in large molecules.
We present the design of the newly constructed cryogenic Fourier-transform ion cyclotron resonance (FT-ICR) ion trap for infrared ion spectroscopy. Trapped ions are collisionally cooled by the pulsed introduction of buffer gas into the cell. Using different buffer gases and cell temperatures, we record action spectra of weakly bound neutral gas-analyte complexes with an IR laser source. We show for the first time that ion-He complexes can be observed in an ICR cell at temperatures around 4 K. We compare the experimental vibrational spectra of Ag(PPh) obtained by tagging with different neutral gases: He, Ne, Ar, H, and N to computed vibrational spectra. Furthermore, the conditions necessary for the formation of neutral tags within an ICR ion trap are studied.
Rapidly developing mid-infrared quantum cascade laser (QCL) technology gives easy access to broadly tunable mid-IR laser radiation at a modest cost. Despite several applications of QCL in the industry, its usage for spectroscopic investigation of synthetically relevant organic compounds has been limited. Here we report the application of an external cavity, continuous wave, mid-IR QCL to cryogenic ion vibrational predissociation spectroscopy (CIVP) to analyze a set of large organic molecules, organometallic complexes, and isotopically labeled compounds. The obtained spectra of test molecules are characterized by high signal-to-noise ratio and low FWHM-values, allowing the assignment of two compounds with just a few wavenumbers difference. Data generated by cw-QCL and spectra produced by another standard Nd:YAG DFG system are compared and discussed.
We report an evaluation of the importance of London dispersion in moderately large (up to 36 heavy atoms) organic molecules by means of a molecular torsion balance whose conformations "weigh" one interaction against another in the absence of solvents. The experimental study, with gas-phase cryogenic ion vibrational predissociation (CIVP) spectroscopy, solid-state Fourier transfer infrared (FT-IR), and single-crystal Xray crystallography, is accompanied by density functional theory calculations, including an extensive search and analysis of accessible conformations. We begin with the unsubstituted molecular torsion balance, and then step up the complexity systematically by adding alkyl groups incrementally as dispersion energy donors (DEDs) to achieve a degree of chemical complexity comparable to what is typically found in transition states for many regio-and stereoselective reactions in organic and organometallic chemistry. We find clear evidence for the small attractive contribution by DEDs, as had been reported in other studies, but we also find that small individual contributions by London dispersion, when they operate in opposition to other weak noncovalent interactions, produce composite effects on the structure that are difficult to predict intuitively, or by modern quantum chemical calculations. The experimentally observed structures, together with a reasonable value for a reference cation−π interaction, indicate that the pairwise interaction between two tert-butyl groups, in the best case, is modest. Moreover, the visualization of the conformational space, and comparison to spectroscopic indicators of the structure, as one steps up the complexity of the manifold of noncovalent interactions, makes clear that in silico predictive ability for the structure of moderately large, flexible, organic molecules falters sooner than one might have expected.
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