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Title: Inverting the Swelling Trends in Modular Self-Oscillating Gels Crosslinked by Redox-Active Metal Bipyridine Complexes

Authors:
 [1];  [2]; ORCiD logo [3]
  1. Wyss Institute for Biologically Inspired Engineering at Harvard University, 60 Oxford Street Cambridge MA 02138 USA
  2. John A. Paulson School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street Cambridge MA 02138 USA
  3. Wyss Institute for Biologically Inspired Engineering at Harvard University, 60 Oxford Street Cambridge MA 02138 USA, John A. Paulson School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street Cambridge MA 02138 USA, Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street Cambridge MA 02138 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1402523
Grant/Contract Number:
SC0005247
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Related Information: CHORUS Timestamp: 2017-10-24 07:21:25; Journal ID: ISSN 1616-301X
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Aizenberg, Michael, Okeyoshi, Kosuke, and Aizenberg, Joanna. Inverting the Swelling Trends in Modular Self-Oscillating Gels Crosslinked by Redox-Active Metal Bipyridine Complexes. Germany: N. p., 2017. Web. doi:10.1002/adfm.201704205.
Aizenberg, Michael, Okeyoshi, Kosuke, & Aizenberg, Joanna. Inverting the Swelling Trends in Modular Self-Oscillating Gels Crosslinked by Redox-Active Metal Bipyridine Complexes. Germany. doi:10.1002/adfm.201704205.
Aizenberg, Michael, Okeyoshi, Kosuke, and Aizenberg, Joanna. 2017. "Inverting the Swelling Trends in Modular Self-Oscillating Gels Crosslinked by Redox-Active Metal Bipyridine Complexes". Germany. doi:10.1002/adfm.201704205.
@article{osti_1402523,
title = {Inverting the Swelling Trends in Modular Self-Oscillating Gels Crosslinked by Redox-Active Metal Bipyridine Complexes},
author = {Aizenberg, Michael and Okeyoshi, Kosuke and Aizenberg, Joanna},
abstractNote = {},
doi = {10.1002/adfm.201704205},
journal = {Advanced Functional Materials},
number = ,
volume = ,
place = {Germany},
year = 2017,
month =
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on October 24, 2018
Publisher's Accepted Manuscript

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  • Pulse radiolysis was used to study Co(I) produced by e/sub aq//sup -/ reduction of Co(II) in aqueous solutions containing 2,2'-bipyridine (bpy) or 4,4'-dimethyl-2,2'-bipyridine (dmb) and a hydroxyl radical scavenger. Six equilibria between CoL/sub n//sup +/ and CoL/sub n//sup 2 +/ pairs were characterized. The absorption maxima and stability constants (log K) of the CoL/sub n//sup +/ species are as follows: Co(bpy)/sub 3//sup +/, 610 nm, 6.9; Co(bpy)/sub 2//sup +/, 570 nm, 7.6; Co(bpy)/sup +/, 670 nm, greater than or equal to 12; Co(dmb)/sub 3//sup +/, 610 nm, 7.3; Co(dmb)/sub 2//sup +/, 500 nm, 8.0; Co(dmb)/sup +/, 660 nm, greater thanmore » or equal to 12. The reduction potentials vs. NHE, based on E/sup 0/ (Co(bpy)/sub 3//sup 2+/+/) = -0.95 V and E/sup 0/(Co(dmb)/sub 3//sup 2+/+/) = -1.07 V, were as follows: Co(bpy)/sub 2//sup 2+/+/, -1.09 V; Co(bpy)/sup 2+/+/, -1.23 V; Co(dmb)/sub 2//sup 2+/+/, -1.17 V; Co(dmb)/sup 2+/+, -1.29 V; Co/sup 2+/+/, less than or equal to -1.6 V. Stability constants were also measured for the Co(II) species in 0.1 M chloride. The log K values are 5.95, 5.27, and 4.60 for Co(bpy)/sup 2 +/, Co(bpy)/sub 2//sup 2 +/, and Co(bpy)/sub 3//sup 2 +/, respectively, and 6.38, 5.92, and 5.25 for Co(dmb)/sup 2 +/, Co(dmb)/sub 2//sup 2 +/, and Co(dmb)/sub 3//sup 2 +/, respectively. The (CH/sub 3/)/sub 2/COH and CO/sub 2//sup -/ radicals, produced by OH oxidation of 2-propanol and formate, react slowly (k approx. 10/sup 6/ to 4 x 10/sup 7/ M/sup -1/ s/sup -1/) with the Co(II) complexes to yield Co(I) and radical-addition products in parallel. 40 references, 8 tables, 3 figures.« less
  • The electrochemical reduction of the [Ru(2, 3-dpp)n(bpy)[sub 3[minus]n]][sup 2+] complexes (n = 1[minus]3), which are extensively used as building blocks for the synthesis of polynuclear compounds, has been investigated at [minus]54[degrees]C in DMF solution up to a limit of [minus]3.1 V vs SCE (dpp is the potential bridging ligand bis(2-pyridyl)pyrazine and bpy is 2, 2'-bipyridine). For comparison purposes, the electrochemical behavior of the free 2, 3-dpp ligand has also been investigated. The results obtained have been discussed and compared with those previously reported for bpy and Ru(bpy)[sub 3][sup 2+]. Convolutive analysis and simulation of the cyclic voltammetric curves have beenmore » performed to obtain the redox potentials in the case of overlapping waves. [Ru(2, 3-dpp)[sub 3]][sup 2+], [Ru(2, 3-dpp)[sub 2](bpy)][sup 2+], and [Ru(2, 3-dpp)(bpy)[sub 2]][sup 2+] display 12, 10, and 8 reduction steps, respectively, in the potential window examined. The corresponding redox series are thus noticeably more extended than those exhibited by [Ru(bpy)[sub 3]][sup 2+] and related complexes not containing bridging-type ligands. The analysis of the genetic diagram which related the redox potentials observed for 2, 3-dpp, [Ru(2, 3-dpp)[sub 3]][sup 2+], [Ru(2, 3-dpp)[sub 2](bpy)][sup 2+], [Ru(2, 3-dpp)(bpy)[sub 2]][sup 2+], [Ru(bpy)[sub 3]][sup 2+], and bpy shows that each redox step in the metal complexes is essentially localized on a specific ligand. A satisfactory assignment of the redox sites has been proposed, and their mutual interactions have been discussed. The results obtained show that in order to arrive at a satisfactory assignment of the redox series for a complex containing redox-active ligands a comparison with the behavior of complexes of the same family is as much instructive as a comparison with the behavior of the free ligands.« less
  • We used the redox-active bis(imino)acenapthene (BIAN) ligand to synthesize homoleptic aluminum, chromium, and gallium complexes of the general formula (BIAN) 3M. The resulting compounds were characterized using X-ray crystallography, NMR, EPR, magnetic susceptibility and cyclic voltammetry measurements and modeled using both DFT and ab initio wavefunction calculations to compare the orbital contributions of main group elements and transition metals in ligand-based redox events. Ultimately, complexes of this type have the potential to improve the energy density and electrolyte stability of grid-scale energy storage technologies, such as redox flow batteries, through thermodynamically-clustered redox events.
  • The syntheses and properties of three new ruthenium(II) complexes based on the ligand 2,2[prime]:4,4[double prime]:4[prime],4[prime][double prime]-quaterpyridyl (qpy) are reported. Each new complex is of the type [Ru(bpy)[sub 2]L][sup n+], where L is the parent qpy ligand or is qpy derivatized by the methylation of one or both of the non-[alpha]-diimine nitrogen atoms and n = 2, 3, or 4. The photophysical and electrochemical properties of the new complex ions are reported. The parent ion [Ru(bpy)[sub 2]qpy][sup 2+] is strongly luminescent and has a relatively long lifetime, e.g. in excess of 1400 ns in acetonitrile solution. In contrast, the lifetime ofmore » the dimethyl derivative [Ru(bpy)[sub 2](qpyme[sub 2])][sup 4+] is less than 100 ns. This dimethylated complex has some novel properties. The excited state produced by M-L excitation to the qpyme[sub 2][sup 2+] ligand can be considered in terms of a Ru(III) core and a positively charged ligand. Typically, the excited states of other ruthenium(II) diimine complexes have had neutral or negatively charged ligands. Further, in structural terms, the complex can be considered as an intramolecular assembly of a ruthenium(II) diimine site and a viologen site. Cyclic voltammetry indicates that the first two electrons added to the complex enter the viologen-like acceptor site constituted by the qpyme[sub 2][sup 2+] ligand.« less