skip to main content


Title: Stepwise reduction of a corannulene-based helical molecular nanographene with Na metal
The chemical reduction of a corannulene-based molecular nanographene, C 76 H 64 (1), with Na metal in the presence of 18-crown-6 afforded the doubly-reduced state of 1. This reduction provokes a distortion of the helicene core and has a significant impact on the aromaticity of the system.  more » « less
Award ID(s):
2003411 1834750
NSF-PAR ID:
10325302
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Chemical Communications
Volume:
58
Issue:
37
ISSN:
1359-7345
Page Range / eLocation ID:
5574 to 5577
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    In this paper, we make partial progress on a function field version of the dynamical uniform boundedness conjecture for certain one-dimensional families ${\mathcal{F}}$ of polynomial maps, such as the family $f_{c}(x)=x^{m}+c$ , where $m\geq 2$ . We do this by making use of the dynatomic modular curves $Y_{1}(n)$ (respectively $Y_{0}(n)$ ) which parametrize maps $f$ in ${\mathcal{F}}$ together with a point (respectively orbit) of period $n$ for $f$ . The key point in our strategy is to study the set of primes $p$ for which the reduction of $Y_{1}(n)$ modulo $p$ fails to be smooth or irreducible. Morton gave an algorithm to construct, for each $n$ , a discriminant $D_{n}$ whose list of prime factors contains all the primes of bad reduction for $Y_{1}(n)$ . In this paper, we refine and strengthen Morton’s results. Specifically, we exhibit two criteria on a prime $p$ dividing $D_{n}$ : one guarantees that $p$ is in fact a prime of bad reduction for $Y_{1}(n)$ , yet this same criterion implies that $Y_{0}(n)$ is geometrically irreducible. The other guarantees that the reduction of $Y_{1}(n)$ modulo $p$ is actually smooth. As an application of the second criterion, we extend results of Morton, Flynn, Poonen, Schaefer, and Stoll by giving new examples of good reduction of $Y_{1}(n)$ for several primes dividing $D_{n}$ when $n=7,8,11$ , and $f_{c}(x)=x^{2}+c$ . The proofs involve a blend of arithmetic and complex dynamics, reduction theory for curves, ramification theory, and the combinatorics of the Mandelbrot set. 
    more » « less
  2. Abstract

    Periods of high soil wetness promote anaerobic processes such as iron (Fe) reduction within soil microsites, with implications for organic matter decomposition, the fate of pollutants, and nutrient cycling. Here we discuss potential Fe reduction rates emerging from an interplay between the timescales of the internal reactions (Fe oxidation and reduction) and external forcings (length of oxic vs. anoxic conditions), and under no organic substrate and microbial population limitations. We compute the upper bound on Fe reduction and the theoretical maximum reduction rate, which would be reached under “resonant conditions,” whereby the timescales of external forcings match the internal timescales of the redox reactions. The variability of soil oxygen is then linked to rainfall frequency and intensity through soil moisture dynamics, allowing us to determine the hydroclimatic conditions that generate oxic/anoxic cycles that most favor Fe reduction. These predictions are applied to an aseasonal tropical (Luquillo, Puerto Rico, USA) and a seasonal subtropical (Calhoun, SC, USA) humid forests. We show that the tropical site maintains a high potential for Fe reduction throughout the year, due to rapid and frequent transitions between predicted oxic and anoxic microsite conditions, with a potential to reduce up to 1,800 mmol kg1soil of Fe per year, while a less humid and seasonal climate in the subtropical site limits maximum reduction rates to 60 mmol kg−1 year−1. This analysis paves the way for a global identification of hot spots of potential Fe reduction using readily available hydroclimatic observations.

     
    more » « less
  3. Abstract

    Chemical reduction of pentacene (C22H14,1) with Group 1 metals ranging from Li to Cs revealed that1readily undergoes a two‐fold reduction to afford a doubly‐reduced12−anion in THF. With the help of 18‐crown‐6 ether used as a secondary coordinating agent, five π‐complexes of12−with different alkali metal counterions have been isolated and fully characterized. This series of complexes enables the first evaluation of alkali‐metal ion binding patterns and structural changes of the12−dianion based on the crystallographically confirmed examples. The difference in coordination of the smallest Li+ion vs. heavier Group 1 congeners has been demonstrated. In addition, the use of benzo‐15‐crown‐5 in the reaction of1with Na metal allowed the isolation of the unique solvent‐separated ion product with a “naked” dianion,12−. The detailed structural analyses of the series revealed the C−C bond alteration and core deformation of pentacene upon two‐fold reduction and complexation. The negative charge localization at the central six‐membered ring of12−identified by theoretical calculations corroborates with the X‐ray crystallographic results. Subsequent in‐depth theoretical analysis provided a detailed description of changes in the electronic structure and aromaticity of pentacene upon reduction.

     
    more » « less
  4. Chemical reduction of highly-twisted 9,10,11,20,21,22-hexaphenyltetrabenzo[a,c,l,n]pentacene (C74H46, 1) was investigated using Li and Cs metals as the reducing agents. The Cs-induced reduction of 1 in the presence of 18-crown-6 ether enabled the isolation of a solvent-separated ion pair (SSIP) with a “naked” monoanion. Upon reduction with Li metal, a double reductive dehydrogenative annulation of 1 was observed to afford a new C74H422– dianion. The latter was shown to undergo a further reduction to C74H424– without additional core transformation. All products were characterized by single-crystal X-ray diffraction and spectroscopic methods. Subsequent in-depth theoretical analysis of one vs. two and four electron uptake by 1 provided insights into how the changes of geometry, aromaticity and charge facilitated the core transformation of twistacene observed upon two-fold reduction. These experimental and theoretical results pave the way to understanding of the reduction-induced core transformations of highly twisted and strained π-systems. 
    more » « less
  5. Biocatalytic technologies are characterized by targeted, rapid degradation of contaminants over a range of environmentally relevant conditions representative of groundwater, but have not yet been integrated into drinking water treatment processes. This work investigated the potential for a hybrid ion-exchange/biocatalytic process, where biocatalysis is used to treat ion-exchange waste brine, allowing reuse of the brine. The reduction rates and the fate of the regulated anions perchlorate and nitrate were tested in synthetic brines and a real-world waste brine. Biocatalysts were applied as soluble protein fractions from Azospira oryzae for perchlorate reduction and Paracoccus denitrificans and Haloferax denitrificans for nitrate reduction. In synthetic 12% brine, the biocatalysts retained activity, with rates of 32.3 ± 6.1 U (μg Mo) −1 for perchlorate ( A. oryzae ) and 16.1 ± 7.1 U (μg Mo) −1 for nitrate ( P. denitrificans ). In real-world waste brine, activities were slightly lower (20.3 ± 6.5 U (μg Mo) −1 for perchlorate and 14.3 ± 3.8 U (μg Mo) −1 for nitrate). The difference in perchlorate reduction was due to higher concentrations of nitrate, bicarbonate, and sulfate in the waste brine. The predominant end products of nitrate reduction were nitrous oxide or dinitrogen gas, depending on the source of the biocatalysts and the salt concentration. These results demonstrate biocatalytic reduction of regulated anions in a real-world waste brine, which could facilitate brine reuse for the regeneration of ion-exchange technologies and prevent reintroduction of these anions and their intermediates into the environment. 
    more » « less