Name: 1,3,5-triphenylbenzene and corannulene as electron receptors for lithium solvated electron solutions
Uploaded: 2016-10-10T13:00:00
Description: Watch this Scientific Journal Video about 1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions at JoVE.com

The authors acknowledge funding from the Singapore Ministry of Education Tier 2 Research Fund (project MOE2013-T2-2-002) for this project.

1. Preparation Procedure for 1,3,5-Triphenylbenzene (1)
<ol>
	<li>Place a mixture of acetophenone (4.0 g, 33.3 mmol) and 100 ml of absolute ethanol into a round bottom three neck 250 ml flask equipped with magnetic stirrer, reflux condenser, nitrogen inlet, bubbler, dropping funnel and thermometer. Add silicon tetrachloride (11.9 g, 8.0 ml, 70.2 mmol, 2.1 eq.) to the mixture in one portion at 0 &#176;C under nitrogen using the dropping funnel.</li>
	<li>Observe the evolution of gaseous hydrogen chloride for 10 min. The...

<ol>
	<li>Tan, K. S., Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Physical-Chemical+and+Electrochemical+Studies+of+the+Lithium+Naphthalenide+Anolyte.">Physical-Chemical and Electrochemical Studies of the Lithium Naphthalenide Anolyte.</a> Electrochim Acta. 180, 629-635 (2015).</li><li>Tan, K. S., Grimsdale, A. C., Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+Characterisation+of+Biphenyl-Based+Lithium+Solvated+Electrons+Solutions.">Synthesis and Characterisation of Biphenyl-Based Lithium Solvated Electrons Solutions.</a> J Phys Chem B. 116, 9056-9060 (2012).</li><li>Rinaldi, A., Tan, K. S., Wijaya, O., Wang, Y., Yazami, R., Menictas, C., Skyllas-Kazacos, M., Lim, T. M., Hughes, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ch.+11.">Ch. 11.</a> Advances in batteries for large- and medium-scale energy storage applications in power systems and electric vehicles. , (2014).</li><li>Wang, Y., Tan, K. S., Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Materials Challenges In Alternative &amp; Renewable Energy (MCARE 2014). , (2014).</li><li>Yazami, R., Tan, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> in 8th annual Li Battery Power. , (2012).</li><li>Yazami, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hybrid+Electrochemical+Generator+With+A+Soluble+Anode.">Hybrid Electrochemical Generator With A Soluble Anode.</a> US patent. , (2010).</li><li>Yazami, R., Tan, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Liquid+Metal+Battery.">Liquid Metal Battery.</a> US patent. , (2015).</li><li>Lim, Z. B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+assessment+of+new+cyclopenta-2,4-dienone+derivatives+for+energy+storage+applications.">Synthesis and assessment of new cyclopenta-2,4-dienone derivatives for energy storage applications.</a> Synthetic Met. 200, 85-90 (2015).</li><li>Butterfield, A. M., Gilomen, B., Siegel, J. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kilogram-Scale+Production+of+Corannulene.">Kilogram-Scale Production of Corannulene.</a> Org. Process Res. Dev. 16, 664-676 (2012).</li><li>Elmorsy, S. S., Pelter, A., Smith, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+direct+production+of+tri-+and+hexa-substituted+benzenes+from+ketones+under+mild+conditions.">The direct production of tri- and hexa-substituted benzenes from ketones under mild conditions.</a> Tetrahedron Lett. 32, 4175-4176 (1991).</li><li>Zabula, A. V., Filatov, A. S., Spisak, S. N., Rogachev, A. Y., Petrukhina, M. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Main+Group+Metal+Sandwich:+Five+Lithium+Cations+Jammed+Between+Two+Corannulene+Tetraanion+Decks.">A Main Group Metal Sandwich: Five Lithium Cations Jammed Between Two Corannulene Tetraanion Decks.</a> Science. 333, 1008-1011 (2011).</li></ol>

For the 1,3,5-triphenylbenzene-based LiSES, a sample with a light color shows that it has a low concentration of solvated electrons. LixTPB(THF)24.7 (for x = 1, 2, 3, 4) demonstrates a behavior in its conductivity versus x similar to that seen for LiSES made from biphenyl and naphthalene1, 2.There is an initial increase in conductivity with increase of Li:PAH ratio from 1 to 2 and a subsequent decrease in conductivity upon further increasing the molar ratio to 3 and 4, with condu...

Lithium solvated electron solutions (LiSES) prepared using simple two-ring polyaromatic hydrocarbons (PAH) such as biphenyl and naphthalene can potentially be utilized as liquid anodes in refuelable lithium cells1-7. In the LiSES, these simple PAH molecules served as the electron receptors for solvated electrons from dissolved metallic lithium.
Progressing from these two-ring systems, the authors have since then carried out conductivity measurement studies on LiSES which are prepared using more complex PAHs, starting with the group of cyclopenta-2,4-dienone derivatives8. These PAHs include larger PAHs (&#62;two benzene rings) and PAHs with substituents incorporated into their aromatic rings. A larger PAH molecule with more than two rings is expected to accommodate more lithium atoms per PAH molecule than either biphenyl or naphthalene thus resulting in LiSES with a higher energy density. The objective of introducing substituents into PAHs is to make the PAH accept electrons more readily and become more stable as polyanions in LiSES.
As part of ongoing efforts to develop LiSES with higher energy density, this paper will report on the characterization of LiSES prepared from corannulene made by the literature procedure9 as well as 1,3,5-triphenylbenzene, TPB synthesized by a slightly modified literature 10. 1,3,5-triphenylbenzene, as shown in Figure 1(1), can be classified as a biphenyl derivative with two additional phenyl rings at positions 3 and 5 of the same ring. Since this molecule has four benzene rings, it should uptake 4 atoms of Li per molecule, which is more than for biphenyl (maximum 2.5 mole equivalents of Li per PAH in 0.5 M solution) and naphthalene (&#60;2.5 mole equivalents of lithium per molecule).
Corannulene is a five-ring PAH arranged into a bowl shape as shown in Figure 1(2). Zabula et al.11 have demonstrated the feasibility of dissolving metallic lithium in a solution of corannulene/tetrahydrofuran (THF) to form a solution with five Li+ ions sandwiched between two stable tetraanions of corannulene.
<img alt="Figure 1" src="/files/ftp_upload/54366/54366fig1.jpg" /> 
Figure 1: The molecular structures of 1,3,5-triphenylbenzene (1) and corannulene (2). 1,3,5-triphenylbenzene is classified as a biphenyl derivative with two additional phenyl rings at positions 3 and 5 of the same ring. Corannulene is a five-ring PAH with its five benzene rings arranged into a bowl shape. <a href="https://www.jove.com/files/ftp_upload/54366/54366fig1large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
Thus, both 1,3,5-triphenylbenzene and corannulene are potential candidates for high energy density LiSES.

<table border="0" cellpadding="0" cellspacing="0" width="1005">
	<tbody>
		<tr height="31">
			<td height="31" style="height:31px;width:479px;">Biphenyl Reagentplus, 99.5%</td>
			<td style="width:136px;">Sigma Aldrich</td>
			<td style="width:187px;">B34656-1KG</td>
			<td style="width:204px;"></td>
		</tr>
		<tr height="31">
			<td height="31" style="height:31px;">Tetrahydrofuran Anhydrous, 99.9%, Inhibi</td>
			<td style="width:136px;">Sigma Aldrich</td>
			<td>401757-100ML</td>
			<td></td>
		</tr>
		<tr height="31">
			<td height="31" style="height:31px;">Iodine, Anhydrous, Beads, -10 Mesh, 99.999% trace metals basis&#160;</td>
			<td style="width:136px;">Sigma Aldrich</td>
			<td>451045-25G</td>
			<td></td>
		</tr>
		<tr height="31">
			<td height="31" style="height:31px;">Lithium iodide, anhydrous, 99.95% (metals basis)</td>
			<td style="width:136px;">Alfa Aesar</td>
			<td>40666</td>
			<td></td>
		</tr>
		<tr height="31">
			<td height="31" style="height:31px;width:479px;">Lithium Ion Conducting Glass ceramics (Diameter 1&#34; x 150 mm)&#160;</td>
			<td style="width:136px;">Ohara</td>
			<td style="width:187px;">LICGC(AG01)</td>
			<td></td>
		</tr>
		<tr height="31">
			<td height="31" style="height:31px;width:479px;">Lithium Foil&#160;</td>
			<td style="width:136px;">Alfa Aesar</td>
			<td style="width:187px;">010769.14</td>
			<td></td>
		</tr>
		<tr height="31">
			<td height="31" style="height:31px;width:479px;">Methanol anhydrous, 99.8%</td>
			<td style="width:136px;">Sigma Aldrich</td>
			<td>322415-100ML&#160;</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;">CompactStat : Electrochemical Analyser with Impedance</td>
			<td style="width:136px;">Ivium Technologies</td>
			<td style="width:187px;">Not Applicable</td>
			<td></td>
		</tr>
		<tr height="31">
			<td height="31" style="height:31px;width:479px;">Cond 3310 Conductivity Meter</td>
			<td style="width:136px;">WTW</td>
			<td style="width:187px;">Not Applicable</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:479px;">Digital Multimeter, Model Fluke 179</td>
			<td style="width:136px;">Fluke Corporation</td>
			<td style="width:187px;">Not Applicable</td>
			<td></td>
		</tr>
		<tr height="120">
			<td height="120" style="height:120px;width:479px;">1,3,5-triphenylbenzene</td>
			<td style="width:136px;">Synthesized from acetpohenone according to procedure described in literature</td>
			<td style="width:187px;"></td>
			<td></td>
		</tr>
		<tr height="31">
			<td height="31" style="height:31px;width:479px;">Silicon tetrachloride</td>
			<td style="width:136px;">Sigma Aldrich</td>
			<td style="width:187px;">215120-100G</td>
			<td></td>
		</tr>
		<tr height="31">
			<td height="31" style="height:31px;width:479px;">acetophenone</td>
			<td style="width:136px;">TCI</td>
			<td style="width:187px;">A0061-500g</td>
			<td></td>
		</tr>
		<tr height="31">
			<td height="31" style="height:31px;width:479px;">Ethanol</td>
			<td style="width:136px;">Merck Millipore</td>
			<td style="width:187px;">1.00983.2511</td>
			<td></td>
		</tr>
	</tbody>
</table>

1,3,5-triphenylbenzene and corannulene as electron receptors for lithium solvated electron solutions

The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using two types of polyaromatic hydrocarbons (PAH), namely 1,3,5-triphenylbenzene and corannulene, as electron receptors. The solid PAHs were first dissolved in tetrahydrofuran (THF) to form a solution. Metallic lithium was then dissolved into these PAH/THF solutions to yield either blue or greenish blue solutions, colors which are indicative of the presence of solvated electrons. Conductivity measurements at ambient temperature carried out on 1,3,5-triphenylbenzene-based LiSES, denoted by LixTPB(THF)24.7 (x = 1, 2, 3, 4), showed an increase of conductivity with increase of Li:PAH ratio from x = 1 to 2. However, the conductivity gradually decreased upon further increasing the ratio. Indeed the conductivity of LixTPB(THF)24.7 for x = 4 is even lower than for x = 1. Such behavior is similar to that of the previously reported LiSES prepared from biphenyl and naphthalene. Conductivity versus temperature measurements on corannulene-based LiSES, denoted by LixCor(THF)247 (x = 1, 2, 3, 4, 5), showed linear relationships with negative slopes, indicating a metallic behavior similar to biphenyl and naphthalene-based LiSES.

Reaction between various amounts of lithium and mixtures of 1,3,5-triphenylbenzene with THF gives greenish blue or deep blue colored solutions as shown in Figure 2. A light color indicates that the particular sample of LiSES has a low concentration of solvated electrons. 1,3,5-triphenylbenzene demonstrates increase of conductivity with increase of Li:PAH ratio from 1 to 2 in 0.5 M THF solution (Table 1). However, conductivity value gradually decreases upon further increasing the molar ra...

Watch this Scientific Journal Video about 1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions at JoVE.com

1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions

The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using 1,3,5-triphenylbenzene (TPB) and corannulene as electron receptors.

The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using two types of polyaromatic ...

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