We gratefully acknowledge support from the National Science Foundation under grant CHE-1552164 for development of the original synthesis and characterization methods presented in this manuscript. During preparation of this manuscript, we acknowledge the following agencies for support of student and postdoctoral salaries: Nayon Park (National Science Foundation, CHE-1552164), Madison Monahan (US Department of Energy, Office of Science, Office of Basic Energy Sciences, as part of the Energy Frontier Research Centers program: CSSAS--The Center for the Science of Synthesis Across Scales under Award Number DE-SC0019288), Andrew Ritchhart (National Science Foundation, CHE-1552164), Max R. Friedfeld (Washington Research Foundation).

CAUTION: Proper personal protective equipment should be worn at all times and the material safety data sheet (MSDS) should be read for each chemical prior to use. All steps should be done air-free, because exposing clusters to air and/or water will degrade clusters or prevent proper formation. Any point at which the reaction flask is open to air, N2 should be flowing vigorously to create a protective blanket over the reagents in the flask. All N2 used should be 99.9% or greater in purity.
1. Preparation of molecular precursors
<ol>
	<li>Purification of ligand precursor 
	NOTE: Myristic acid can be substituted by phenylacetic, oleic, or other long-chain carboxylic acids.
	<ol>
		<li>Place a 100 mL 3-neck flask, a stir bar, a reflux condenser, a glass stopper, a thermowell, a T-adapter, and a hose adapter into a 160 &#176;C oven overnight. 
		NOTE: Glassware can also be flame dried and placed in the oven for 1 h.</li>
		<li>Set up the flask, condenser, and thermowell on a Schlenk line while the glassware is still warm using high temperature vacuum grease to ensure glassware remains water-free. Close the final neck of the flask with a rubber septum.</li>
		<li>Place 2.65 g of myristic acid (HO2C14H27, 11.6 mmol) into the flask and flush with N2. Put the flask under vacuum for 2 h with mild stirring at 120 &#176;C to remove residual water from the acid.</li>
	</ol>
	</li>
	<li>Preparation of indium myristate (In(O2C14H27)3) 
	NOTE: Equivalent InP clusters can be prepared with trimethylindium or indium acetate.
	<ol>
		<li>Preparation via trimethylindium (InMe3)
		<ol>
			<li>Weigh out 0.512 g of InMe3 (3.2 mmol, anhydrous) and dissolve it in 10 mL of anhydrous toluene. Draw the solution into a syringe and seal with a rubber septum to keep the solution air-free during removal from the glovebox.</li>
			<li>Add 10 mL of anhydrous toluene to myristic acid from step 1.1 via a syringe and stir at room temperature until dissolved.</li>
			<li>Slowly add InMe3 from step 1.2.1.1 via a syringe (~2 drops/s) while stirring. This step should result in rapid gas formation visible to the eye. Allow to stir for 10 min to ensure complete reaction.</li>
		</ol>
		</li>
		<li>Preparation via indium acetate (In(OAc)3)
		<ol>
			<li>Weigh out 0.93 g of In(OAc)3 (3.2 mmol) and add to the flask containing myristic acid from step 1.1 under positive N2 flow.</li>
			<li>Evacuate the flask and heat the flask to 100 &#176;C while stirring. The mixture should melt. Let the solution off-gas acetic acid for 12 h (overnight) at 120 &#176;C.</li>
			<li>Refill the flask with N2 and add 20 mL of anhydrous toluene via a syringe through the rubber septum.</li>
		</ol>
		</li>
	</ol>
	</li>
</ol>
2. Synthesis of In37P20(O2CR)51
<ol>
	<li>Heat the reaction flask containing In(O2C14H27)3 solution to 110 &#176;C.</li>
	<li>Add 465 &#956;L of P(SiMe3)3 (1.6 mmol) to 10 mL of anhydrous toluene in the glovebox. Draw the solution into a syringe and insert the needle into a rubber stopper until the needle opening is completely covered. Be cautious when removing from the glovebox as P(SiMe3)3 is a pyrophoric liquid.</li>
	<li>Rapidly inject the P(SiMe3)3 solution into the hot In(O2C14H27)3 solution. The solution should turn yellow quickly after the addition of P(SiMe3)3. Monitor the reaction by taking 50 &#956;L aliquots of reaction solution into 3 mL of toluene for UV-Vis analysis. The reaction is finished when no further changes are seen in the aliquot spectra.</li>
	<li>Remove from heat to cool the flask and halt the reaction. 
	NOTE: The growth of InP clusters is optimal at a temperature range of 100-110 &#176;C. The reaction proceeds at lower temperatures, including room temperature, but goes very slowly. Higher temperatures result in evolution of quantum dots of varying sizes depending on the temperature. The reaction typically requires 20-60 min to go to completion, depending on the ligands used. Failure to run the reaction to completion could result in small, unstable clusters that will quickly decompose. Running the reaction past completion will not alter the cluster composition as long as the temperature is at or below 110 &#176;C.</li>
</ol>
3. Workup of In37P20(O2CR)51
NOTE: All solvents used in the purification steps are anhydrous and stored over 4 &#197; sieves in the N2-filled glovebox.
<ol>
	<li>Isolation of In37P20(O2CR)51
	<ol>
		<li>Remove the solvent from the cluster solution under reduced pressure on the Schlenk line.</li>
		<li>Seal the flask under N2 using the glass stopper and T-adapter from the oven. Fasten the flask and adapters with electrical tape and bring into the glovebox.</li>
	</ol>
	</li>
	<li>Purification via precipitation, centrifugation, and re-dissolution
	<ol>
		<li>Resuspend the clusters in minimal toluene (~1 mL) and centrifuge to remove solid impurities (7,197 x g, 10 min). Decant and keep the clear, yellow supernatant and discard any solids.</li>
		<li>Add 3 mL of acetonitrile (3:1, MeCN:tol) to the supernatant to precipitate the clusters (yellow precipitate) and centrifuge again under the same parameters. Discard the clear, colorless supernatant and resuspend the yellow solid pellet of clusters in minimal toluene.</li>
		<li>Repeat step 3.2.2 for a total of 5 cycles.</li>
	</ol>
	</li>
	<li>Purification via column
	<ol>
		<li>Take the clusters dissolved in minimal toluene (~0.5 mL) and apply them in a thin band to a freshly cleaned size-exclusion, liquid column (60 cm, 25 mm) packed with permeable gel beads (see Table of Materials) using toluene as the solvent.</li>
		<li>Allow the clusters to run through the column ensuring to keep the beads wet by adding fresh toluene as the liquid runs through the column. Collect all yellow fluid but make sure to stop collecting immediately after the yellow passes as excess ligand will come off after the cluster. Typically, the clusters take about 20 min to elute at room temperature. 
		NOTE: To confirm where the cluster region ends on the column, a laser pointer (405 nm) can be used to see where glowing resumes. The portion of the column containing clusters will not glow.</li>
		<li>Remove solvent under reduced pressure via a vacuum pump until a waxy solid is achieved. Store dry clusters under N2 for best stability. In a typical synthesis, 1.2 g of clusters should be isolated, representing a 90% yield.</li>
	</ol>
	</li>
</ol>
4. Synthesis of InP quantum dots using In37P20(O2CR)51 as a single source precursor
NOTE: Indium phosphide quantum dots can be synthesized from purified InP clusters using a heat-up or hot injection method.
<ol>
	<li>Heat-up method
	<ol>
		<li>Degas a 100 mL 3-neck round bottom flask equipped with a stir bar, a glass thermowell, a T-adapter, and a rubber septum. Assemble the glassware using high temperature vacuum grease.</li>
		<li>Dissolve 200 mg of purified InP clusters in 20 mL of anhydrous 1-octadecene. Inject the InP cluster solution into the reaction flask via a syringe under a positive N2 flow, followed by an additional 20 mL of anhydrous 1-octadecene. Briefly degas to ensure the reaction flask is air-free.</li>
		<li>Heat the solution to 300 &#176;C under a positive N2 flow while stirring. The growth of QDs can be monitored by UV-Vis spectroscopy with timed aliquots. The bright yellow color persists up to around 200 &#176;C and changes from yellow to bright orange to dark red-brown. The reaction is complete in 30-40 min.</li>
		<li>Cool down the reaction flask to room temperature by removing the heating mantle. The solution after cooling displays an optically clear red color. Remove 1-octadecene by vacuum distillation at 160 &#176;C. Replace the appropriate glassware as quickly as possible to limit air exposure.</li>
		<li>Dissolve InP QDs using minimal amount (&#60;5 mL) of anhydrous toluene in a N2-filled glovebox. Transfer the crude solution to a centrifuge tube. Add ~40 mL of anhydrous acetonitrile and centrifuge for purification (7,197 x g, 10 min).</li>
		<li>Pour off the supernatant and re-dissolve the precipitate in approximately 5 mL of anhydrous toluene. Repeat the purification steps for a total of 3 cycles. Store the purified product dissolved in anhydrous toluene.</li>
	</ol>
	</li>
	<li>Hot-injection method
	<ol>
		<li>Degas a 100 mL 3-neck round bottom flask equipped with a thermowell, a Schlenk adapter, and a rubber septum. Assemble the glassware using high temperature vacuum grease.</li>
		<li>Inject 35 mL of anhydrous 1-octadecene into the reaction flask. Heat the solvent to 300 &#176;C under inert gas while stirring.</li>
		<li>Dissolve 200 mg of purified InP clusters in 5 mL of anhydrous 1-octadecene and inject the cluster solution into the reaction flask. The reaction is complete in 15-20 min.</li>
		<li>Cool down the solution to room temperature by removing the heating mantle. Distill off 1-octadecene and purify InP QDs as described in steps 4.1.5 to 4.1.6.</li>
	</ol>
	</li>
</ol>
5. Characterization of In37P20(O2CR)51 and InP quantum dots
<ol>
	<li>Transmission electron microscopy (TEM)
	<ol>
		<li>Prepare a dilute solution of cluster (~5 mg) or quantum dots in pentane:toluene (1:1, 2 mL total). Solution color should be barely visible.</li>
		<li>Pick up a lacey carbon TEM grid (400 mesh, ultra-fine) with tweezers and place off the edge of a surface, making sure the grid is not touching anything besides the tweezers.</li>
		<li>Drop-cast one large drop onto the grid and let it dry completely with no dabbing away solution (~20 min). Place the grid under vacuum and let further dry overnight.</li>
		<li>Image the sample with TEM. Typical image conditions include spot size 5,200 kV electron beam, objective aperture completely open, and magnification of 350,000X.</li>
		<li>In the native image format (.dm3), measure the particle size using the straight-line tool to create a line across the imaged particle (see Table of Materials for software). The command tool finder will give a length in nanometers corresponding to the drawn line, when the line is actively being dragged or clicked on and measure the particle diameter.</li>
	</ol>
	</li>
	<li>Nuclear magnetic resonance (NMR) 
	NOTE: 1H NMR needs as little as 20 mg of clusters, but 31P NMR requires at least 40 mg of clusters to resolve the cluster region.
	<ol>
		<li>Prepare cluster solution (40 mg) in deuterated benzene (C6D6, ~0.7 mL) in the glovebox and transfer the solution into an oven-dried J-young NMR tube. Seal the tube under N2 and remove from the glovebox for measurements.</li>
		<li>Collect 1H NMR spectra on a 300 MHz or greater instrument. Common parameters include 2 dummy scans, 6 scans, and 30 s delay time.</li>
		<li>Collect 31P NMR spectra on a 500 MHz or greater instrument. Use a phosphoric acid standard to calibrate the instrument prior to use. Common parameters include an offset of -100 ppm, sweep width of 500 ppm, and 256 scans repeated 40 times (about 14 h of total run time to ensure a strong enough signal).</li>
	</ol>
	</li>
	<li>X-ray Diffraction (XRD)
	<ol>
		<li>Prepare a highly concentrated solution of clusters or quantum dots by either dissolving dried material in minimal toluene (&#60; 1 mL) or removing toluene from a stock solution.</li>
		<li>Drop-cast onto an oven-dried Si wafer and let dry for ~30 min. For consistency of drop size, use a digital micropipette with the setting at 3~5 &#181;L. Repeat 2-3 times until a film of clusters or quantum dots has sufficiently set.</li>
		<li>Collect XRD data from 10 to 70&#176; with 5.5&#176; intervals. Set each interval to 30 s acquisition time for a quick run or 240 s acquisition for higher resolution.</li>
	</ol>
	</li>
	<li>Photoluminescence (PL)
	<ol>
		<li>Transfer the solution for PL analysis into a 1 x 1 cm quartz fluorescence spectrophotometer cell.</li>
		<li>Set the excitation at 450 nm and the monochromator slit widths for both entrance and exit slits at 3 nm. Set the integration time at 0.1 s/nm or 1 s/nm for higher resolution.</li>
	</ol>
	</li>
</ol>

<ol>
	<li>Shirasaki, Y., Supran, G. J., Bawendi, M. G., Bulovi&#263;, V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Emergence+of+Colloidal+Quantum-Dot+Light-Emitting+Technologies.">Emergence of Colloidal Quantum-Dot Light-Emitting Technologies.</a> Nature Photonics. 7, 13-23 (2013).</li><li>Shea-Rohwer, L. E., Martin, J. E., Cai, X., Kelley, D. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Red-Emitting+Quantum+Dots+for+Solid-State+Lighting.">Red-Emitting Quantum Dots for Solid-State Lighting.</a> ECS Journal of Solid State Science and Technology. 2, R3112-R3118 (2013).</li><li>Kazlas, P. T., Linton, J. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Quantum+Dot-Based+Light+Sheets+Useful+for+Solid-State+Lighting.">Quantum Dot-Based Light Sheets Useful for Solid-State Lighting.</a> , (2010).</li><li>Kairdolf, B. A., Smith, A. M., Stokes, T. H., Wang, M. D., Young, A. N., Nie, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Semiconductor+Quantum+Dots+for+Bioimaging+and+Biodiagnostic+Applications.">Semiconductor Quantum Dots for Bioimaging and Biodiagnostic Applications.</a> Annual Review of Analytical Chemistry. 6, 143-162 (2013).</li><li>Petryayeva, E., Algar, W. R., Medintz, I. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Quantum+Dots+in+Bioanalysis:+A+Review+of+Applications+across+Various+Platforms+for+Fluorescence+Spectroscopy+and+Imaging.">Quantum Dots in Bioanalysis: A Review of Applications across Various Platforms for Fluorescence Spectroscopy and Imaging.</a> Applied Spectroscopy. 67, 215-252 (2013).</li><li>Sambur, J. B., Chen, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Approaches+to+Single-Nanoparticle+Catalysis.">Approaches to Single-Nanoparticle Catalysis.</a> Annual Review of Physical Chemistry. 65, 395-422 (2014).</li><li>Xia, Y., Yang, H., Campbell, C. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanoparticles+for+Catalysis.">Nanoparticles for Catalysis.</a> Accounts of Chemical Research. 46, 1671-1672 (2013).</li><li>Lewis, N. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Toward+Cost-Effective+Solar+Energy+Use.">Toward Cost-Effective Solar Energy Use.</a> Science. 315, 798-801 (2007).</li><li>Semonin, O. E., Luther, J. M., Beard, M. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Quantum+Dots+for+Next-Generation+Photovoltaics.">Quantum Dots for Next-Generation Photovoltaics.</a> Materials Today. 15, 508-515 (2012).</li><li>Carey, G. H., Abdelhady, A. L., Ning, Z., Thon, S. M., Bakr, O. M., Sargent, E. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Colloidal+Quantum+Dot+Solar+Cells.">Colloidal Quantum Dot Solar Cells.</a> Chemical Reviews. 115, 12732-12763 (2015).</li><li>Colegrove, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Quantum+Dot+Technology+Supply+Chain+and+Market+Forecast.">Quantum Dot Technology Supply Chain and Market Forecast.</a> Display Research. , (2018).</li><li>Pu, Y., Cai, F., Wang, D., Wang, J. X., Chen, J. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Colloidal+Synthesis+of+Semiconductor+Quantum+Dots+toward+Large-Scale+Production:+A+Review.">Colloidal Synthesis of Semiconductor Quantum Dots toward Large-Scale Production: A Review.</a> Industrial Engineering Chemical Research. 57, 1790-1802 (2018).</li><li>Gary, D. C., Terban, M. W., Billinge, S. J. L., Cossairt, B. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Two-Step+Nucleation+and+Growth+of+InP+Quantum+Dots+via+Magic-Sized+Cluster+Intermediates.">Two-Step Nucleation and Growth of InP Quantum Dots via Magic-Sized Cluster Intermediates.</a> Chemistry of Materials. 27, 1432-1441 (2015).</li><li>Cossairt, B. M., Owen, 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=CdSe+Clusters:+At+the+Interface+of+Small+Molecules+and+Quantum+Dots.">CdSe Clusters: At the Interface of Small Molecules and Quantum Dots.</a> Chemistry of Materials. 23, 3114-3119 (2011).</li><li>Zhang, J., 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=Evolution+of+Self-Assembled+ZnTe+Magic-Sized+Nanoclusters.">Evolution of Self-Assembled ZnTe Magic-Sized Nanoclusters.</a> Journal of the American Chemical Society. 137, 742-749 (2015).</li><li>Zhu, T., 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=Two-Step+Nucleation+of+CdS+Magic-Size+Nanocluster+MSC-311.">Two-Step Nucleation of CdS Magic-Size Nanocluster MSC-311.</a> Chemisty of Materials. 29, 5727-5735 (2017).</li><li>Gary, D. C., Flowers, S. E., Kaminsky, W., Petrone, A., Li, X., Cossairt, B. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Single-Crystal+and+Electronic+Structure+of+a+1.3+Nm+Indium+Phosphide+Nanocluster.">Single-Crystal and Electronic Structure of a 1.3 Nm Indium Phosphide Nanocluster.</a> Journal of the American Chemical Society. 138, 1510-1513 (2016).</li><li>Janke, E. M., 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=Origin+of+Broad+Emission+Spectra+in+InP+Quantum+Dots:+Contributions+from+Structural+and+Electronic+Disorder.">Origin of Broad Emission Spectra in InP Quantum Dots: Contributions from Structural and Electronic Disorder.</a> Journal of the American Chemical Society. 140, 15791-15803 (2018).</li><li>Stein, J. L., 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=Probing+Surface+Defects+of+InP+Quantum+Dots+Using+Phosphorus+K&#945;+and+K&#946;+X-Ray+Emission+Spectroscopy.">Probing Surface Defects of InP Quantum Dots Using Phosphorus K&#945; and K&#946; X-Ray Emission Spectroscopy.</a> Chemistry Materials. 30, 6377-6388 (2018).</li><li>Giansante, C., Infante, I. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Surface+Traps+in+Colloidal+Quantum+Dots:+A+Combined+Experimental+and+Theoretical+Perspective.">Surface Traps in Colloidal Quantum Dots: A Combined Experimental and Theoretical Perspective.</a> Journal of Physical Chemistry Letters. 8, 5209-5215 (2017).</li><li>Tessier, M. D., 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=Interfacial+Oxidation+and+Photoluminescence+of+InP-Based+Core/Shell+Quantum+Dots.">Interfacial Oxidation and Photoluminescence of InP-Based Core/Shell Quantum Dots.</a> Chemistry of Materials. 30, 6877-6883 (2018).</li><li>Brown, R. P., Gallagher, M. J., Fairbrother, D. H., Rosenzweig, Z. <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+Degradation+of+Cadmium-Free+InP+and+InPZn/ZnS+Quantum+Dots+in+Solution.">Synthesis and Degradation of Cadmium-Free InP and InPZn/ZnS Quantum Dots in Solution.</a> Langmuir. 34, 13924-13934 (2018).</li><li>Brodu, A., 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=Exciton+Fine+Structure+and+Lattice+Dynamics+in+InP/ZnSe+Core/Shell+Quantum+Dots.">Exciton Fine Structure and Lattice Dynamics in InP/ZnSe Core/Shell Quantum Dots.</a> ACS Photonics. 5, 3353-3362 (2018).</li><li>Yang, J., 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=Chemical+Synthesis,+Doping,+and+Transformation+of+Magic-Sized+Semiconductor+Alloy+Nanoclusters.">Chemical Synthesis, Doping, and Transformation of Magic-Sized Semiconductor Alloy Nanoclusters.</a> Journal of the American Chemical Society. 139, 6761-6770 (2017).</li><li>Xie, L., Harris, D. K., Bawendi, M. G., Jensen, K. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effect+of+Trace+Water+on+the+Growth+of+Indium+Phosphide+Quantum+Dots.">Effect of Trace Water on the Growth of Indium Phosphide Quantum Dots.</a> Chemistry of Materials. 27 (14), 5058-5063 (2015).</li><li>Gary, D. C., Petrone, A., Li, X., Cossairt, B. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Investigating+the+Role+of+Amine+in+InP+Nanocrystal+Synthesis:+Destabilizing+Cluster+Intermediates+by+Z-Type+Ligand+Displacement.">Investigating the Role of Amine in InP Nanocrystal Synthesis: Destabilizing Cluster Intermediates by Z-Type Ligand Displacement.</a> Chemical Communications. 53 (1), 161-164 (2017).</li><li>De Roo, J., 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=Probing+Solvent-Ligand+Interactions+in+Colloidal+Nanocrystals+by+the+NMR+Line+Broadening.">Probing Solvent-Ligand Interactions in Colloidal Nanocrystals by the NMR Line Broadening.</a> Chemistry of Materials. 30 (15), 5485-5492 (2018).</li><li>Kirkwood, N., 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=Finding+and+Fixing+Traps+in+II-VI+and+III-V+Colloidal+Quantum+Dots:+The+Importance+of+Z-Type+Ligand+Passivation.">Finding and Fixing Traps in II-VI and III-V Colloidal Quantum Dots: The Importance of Z-Type Ligand Passivation.</a> Journal of the American Chemical Society. 140 (46), 15712-15723 (2018).</li><li>Ritchhart, A., Cossairt, B. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Templated+Growth+of+InP+Nanocrystals+with+a+Polytwistane+Structure.">Templated Growth of InP Nanocrystals with a Polytwistane Structure.</a> Angewandte Chemie International Edition. 57 (7), 1908-1912 (2018).</li><li>Friedfeld, M. R., Johnson, D. A., Cossairt, B. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Conversion+of+InP+Clusters+to+Quantum+Dots.">Conversion of InP Clusters to Quantum Dots.</a> Inorganic Chemistry. 58 (1), 803-810 (2019).</li><li>Gary, D. C., Cossairt, B. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Role+of+Acid+in+Precursor+Conversion+During+InP+Quantum+Dot+Synthesis.">Role of Acid in Precursor Conversion During InP Quantum Dot Synthesis.</a> Chemistry of Materials. 25 (12), 2463-2469 (2013).</li><li>Becker, G., 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=.">.</a> Inorganic Synthesis. 27, 243-249 (1990).</li></ol>

The authors have nothing to disclose.

The synthesis of InP magic-sized clusters and their conversion into quantum dots follow straightforward procedures that have been shown to consistently produce high quality samples. The ability to synthesize and isolate InP clusters as an intermediate has distinct advantages in terms of subjecting these nanostructures to modifications that can be well-characterized and consequently be incorporated in the final QDs. The atomically precise nature of the clusters and the high reproducibility provide a platform for innovative studies in surface modifications, defects, and alloying of the InP systems and open doors to a wide range of applications such as in displays, solid-state lighting, catalysis, and photovoltaics.
In the synthesis of InP clusters, it is critical that all reagents are of high purity and thoroughly dried, as the success of the synthesis is contingent upon water- and air-free experimental conditions and purity of the precursors for uniform growth in high yields. Additionally, it is recommended that sufficient precautions are taken when handling P(SiMe3)3, which is light-sensitive and pyrophoric. This reagent should be stored in a light-, air-, and water-free environment and caution should be taken to prevent air and water exposure before and during the reaction. For efficient growth of the clusters, the temperature range should be 100-110 &#176;C; at room temperature, the growth is extremely slow, and a higher temperature will result in conversion into quantum dots of varying sizes depending on the temperature. The presented protocol is also highly scalable and versatile, allowing synthetic control and modifications through a breadth of parameters. The myristic acid used as the ligands for InP clusters and subsequent QDs can be replaced by phenylacetic acid, oleic acid, or other short and long-chain carboxylic acids. Post-synthetic addition of P(SiMe3)3 to solutions of InP clusters that have slightly perturbed absorption features (red-shifted and/or broadened) has been observed to result in a size focusing effect where the consumption of excess indium myristate results in a ~3 nm blueshift in the absorption spectra29.
The purification method of the clusters has been empirically optimized in our lab to avoid oxidation and to isolate the highest possible yields. The choice of acetonitrile as the antisolvent and its volume ratio with toluene fulfill these goals. Finally, the clusters are resuspended in minimal amount of toluene and centrifuged to remove any solid impurities that may have resulted during synthesis. Removing toluene from the final solution gives a yellow paste that can be stored for at least 36 months under air- and water-free conditions. It should also be noted in regard to preparing NMR samples for characterization of the purified product that the precise chemical shifts for the 11 distinct resonances in 31P NMR spectrum vary depending on the identity of the indium precursors. Furthermore, insufficient purification and variation in cluster concentration can result in line broadening. In order to obtain a clean spectrum with sharp features, it is suggested that at least 40 mg of the cluster is dissolved in a minimal amount of anhydrous C6D6 (~0.7 mL).
Similarly, the synthesis of InP QDs via clusters must be performed under water- and air-free conditions. Previous studies have shown that the presence of water in indium precursors and the addition of trace amounts of water or hydroxide lead to significant changes in the growth of InP QDs and the surface chemistry of the final product25. When running the reaction at a different scale than described in the protocol, it should be noted that for the hot-inject method, the cluster solution for injection should be sufficiently concentrated and the volume should be smaller compared to the heated solvent in the flask. This is to minimize the abrupt decrease in temperature as the reaction temperature profile plays a nontrivial role in the synthesis. Detailed work on the conversion mechanism of InP clusters to QDs has been recently reported where the effects of the addition of different precursors (i.e., carboxylic acid, indium carboxylate), temperatures, and concentration have been explored30. Through these studies, it has been revealed that thermolysis temperatures &#62; 220 &#176;C are required for obtaining high yields of optimal quality QDs. The purification of InP QDs follows similar logic and process as mentioned above for the clusters, except that the storage of purified QDs is recommended in solution with a solvent such as toluene. In solid form, the QDs have been observed to form aggregates over time, preventing homogeneous colloidal dispersion. One final note regarding the protocol is that removing 1-octadecene by vacuum distillation after the synthesis of InP QDs rather than by only precipitation-redissolution is a recommended first step of QD purification. This is to limit the volume of solvent required in the workup and because the residual ODE may interdigitate with the long-chain carboxylate ligand shell, causing difficulties with sample preparation for characterization and subsequent use.
We have demonstrated the synthesis and characterization of atomically-precise InP magic-size clusters, In37P20(O2CR)51, and their use as single source precursors for the synthesis of InP quantum dots using both heat-up and hot-injection methods. The reported synthesis of InP clusters is versatile and can be generalized to a wide range of alkyl carboxylate ligands. The synthesis of the InP QDs from the clusters provides a highly reproducible method for the synthesis of these challenging nanostructures with high quality in terms of size distribution and crystallinity. Opportunities abound for further elaboration of this method through post-synthetic modification of the clusters themselves and for engineering the cluster to quantum dot conversion strategy. Because of this, we believe these methods are useful and potentially technologically meaningful for the synthesis of InP and related emissive materials for display and lighting applications.

An erratum was issued for: <a href="https://jove.unicartagenaproxy.elogim.com/video/59425/synthesis-in37p20-o2cr-51-clusters-their-conversion-to-inp-quantum">Synthesis of In37P20(O2CR)51 Clusters and Their Conversion to InP Quantum Dots</a>.&#160; The Representative Results&#160;were&#160;updated.
The fifth sentence in the second paragraph of the Representative Results was updated from:
The 31P NMR spectrum of myristate-capped InP clusters shows 11 distinct peaks (2 P atoms on the C2 axis that each give a unique peak and the remaining 18 P each have a symmetry equivalent, resulting in an additional 9 peaks) ranging from -256 to -311 ppm (Figure 1d)26.
to:
The 31P NMR spectrum of myristate-capped InP clusters shows 11 distinct peaks (2 P atoms on the C2 axis that each give a unique peak and the remaining 18 P each have a symmetry equivalent, resulting in an additional 9 peaks) ranging from -187&#160;to -242&#160;ppm (Figure 1d)26.&#160;
Figure 1 in the Representative Results was updated from:
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/59425/59425fig1.jpg" />
to:
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/59425/59425fig1v2.jpg" />

An erratum was issued for: <a href="https://jove.unicartagenaproxy.elogim.com/video/59425/synthesis-in37p20-o2cr-51-clusters-their-conversion-to-inp-quantum">Synthesis of In37P20(O2CR)51 Clusters and Their Conversion to InP Quantum Dots</a>.&#160; The Representative Results&#160;were&#160;updated.

Erratum: Synthesis of In37P20(O2CR)51 Clusters and Their Conversion to InP Quantum Dots

Colloidal semiconductor quantum dots have seen an acceleration in synthetic development over the previous three decades owing to their potential in a variety of optoelectronic applications including displays1, solid-state lighting2,3, biological imaging4,5, catalysis6,7, and photovoltaics8,9,10. Given their recent commercial success in the area of wide-color gamut displays, the quantum dot market is expected to exceed 16 billion dollars by 202811. A significant shift in material focus from the II-VI (and IV-VI) to the III-V family has occurred in the last several years as the search for less toxic, Cd and Pb-free alternatives for use in highly distributed electronics applications has begun. Indium phosphide in particular has been identified as a leading drop-in replacement for CdSe12. It has become apparent, however, that optimization of InP-based quantum dots is more difficult and does not always benefit from the same methods used for the more well-established chalcogenide materials. This is primarily because the nucleation and growth profile of InP nanoparticles follows a non-classical, two-step mechanism13. This mechanism is invoked due to the intermediacy of locally stable, atomically precise intermediates known as &#8220;magic-sized&#8221; clusters14,15,16. In particular, In37P20(O2CR)51 has been identified as one key, isolable intermediate in the synthesis of InP from P(SiMe3)3, indium carboxylate, and carboxylic acid17.
The presence of this intermediate on the reaction coordinate has many tangible effects on the growth of InP nanostructures. The existence of cluster intermediates themselves invalidates classical concepts of nucleation and growth based on the La Mer model and means that optimizing reaction conditions such as concentration, temperature, and precursor may not achieve sufficiently uniform ensemble properties. Rather, it has been shown that the use of the InP cluster as a single-source precursor results in highly monodisperse quantum dots with narrow optical features13. Recent literature has suggested that monodispersity, however, is not the only factor limiting InP&#8217;s parity with other optoelectronic materials18. Surface defects, oxidation, and alloying are critical factors still under intense research that will require significant innovation for optimized InP architectures19,20,21,22,23,24. The atomically precise nature of clusters, such as In37P20(O2CR)51, makes them ideal platforms for probing the consequences of many post-synthetic surface modifications. Normally, ensemble inhomogeneity of nanoparticles makes determining surface and compositional effects difficult, but because the cluster of InP is known to be atomically precise, both compositionally and crystallographically, it is an ideal model system.
The synthesis of the In37P20(O2CR)51 cluster is no more difficult than the synthesis of more widely used nanoparticles such as CdSe, PbS, or ZnO. It requires only standard glassware, widely available chemicals, and basic knowledge of air-free Schlenk and glovebox techniques. The procedure itself can be done on the gram scale and with yields in excess of 90%. As we will show, the successful synthesis of InP cluster is not &#8220;magic&#8221; but rather an exercise in fundamentals. Pure reagents, dry glassware, proper air-free techniques, and attention to detail are all that is required to access this atomically precise nanocluster. Moreover, we also elaborate on ideal methods for its conversion to highly crystalline InP quantum dots with narrow size distributions.

<table>
	<tbody>
		<tr>
			<td>Acetonitrile, anhydrous, 99.8%</td>
			<td>Sigma Aldrich</td>
			<td>271004</td>
			<td>Dried over 4&#197; sieves</td>
		</tr>
		<tr>
			<td>Adapter, Airfree, 14/20 Joint, 0 - 4mm Chem-Cap (T-adapter)</td>
			<td>Chemglass Life Sciences LLC</td>
			<td>AF-0501-01</td>
			<td></td>
		</tr>
		<tr>
			<td>Adapter, Inlet, 14/20 Inner Joint</td>
			<td>Chemglass Life Sciences LLC</td>
			<td>CG-1014-14</td>
			<td></td>
		</tr>
		<tr>
			<td>Bio-Beads S-X1, 200-400 mesh</td>
			<td>Bio-Rad Laboratories</td>
			<td>152-2150</td>
			<td></td>
		</tr>
		<tr>
			<td>Cary 5000 UV-Vis-NIR</td>
			<td>Agilent</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Column, Chromatography, 24/40 Outer Joint, 3/4in ID X 10in E.L., 2mm Stpk</td>
			<td>Chemglass Life Sciences LLC</td>
			<td>CG-1188-06</td>
			<td></td>
		</tr>
		<tr>
			<td>Condenser, Liebig, 185mm, 
			14/20 Top Outer, 14/20 Lower Inner, 110mm Jacket Length</td>
			<td>Chemglass Life Sciences LLC</td>
			<td>CG-1218-A-20</td>
			<td></td>
		</tr>
		<tr>
			<td>Distilling heads, short paths, jacketed</td>
			<td>Chemglass Life Sciences LLC</td>
			<td>CG-1240</td>
			<td></td>
		</tr>
		<tr>
			<td>Eppendorf&#160;Microcentrifuge 5430</td>
			<td>Fisher Chemical</td>
			<td>05-100-177</td>
			<td></td>
		</tr>
		<tr>
			<td>Falcon 15mL Conical Centrifuge Tubes</td>
			<td>Fisher Chemical</td>
			<td>14-959-49B</td>
			<td></td>
		</tr>
		<tr>
			<td>Flask, Round Bottom, 50mL, Heavy Wall, 14/20 - 14/20, 3-Neck, Angled 20&#176;</td>
			<td>Chemglass Life Sciences LLC</td>
			<td>CG-1524-A-05</td>
			<td></td>
		</tr>
		<tr>
			<td>ImageJ</td>
			<td>Developed at National Institutes of Health&#160;and the Laboratory for Optical and Computational Instrumentation</td>
			<td></td>
			<td>Open source Java image processing program</td>
		</tr>
		<tr>
			<td>Indium acetate, 99.99%</td>
			<td>Sigma Aldrich</td>
			<td>510270</td>
			<td></td>
		</tr>
		<tr>
			<td>Myristic acid, 99%</td>
			<td>Sigma Aldrich</td>
			<td>M3128</td>
			<td></td>
		</tr>
		<tr>
			<td>Temperature controller</td>
			<td>Fisher Chemical</td>
			<td>50 401 831</td>
			<td></td>
		</tr>
		<tr>
			<td>Thermometers, non-mercury, 10/18</td>
			<td>Chemglass Life Sciences LLC</td>
			<td>CG-3508-N</td>
			<td></td>
		</tr>
		<tr>
			<td>Thermowell, 14/20 Inner Jt, 1/2&#34; OD above the Jt, 6mm OD Round Bottomed Tube below the Jt, for 25ml RBF</td>
			<td>Chemglass Life Sciences LLC</td>
			<td>UW-1205-171JS</td>
			<td>Custom ordered</td>
		</tr>
		<tr>
			<td>Toluene, anhydrous, 99.8%</td>
			<td>Sigma Aldrich</td>
			<td>244511</td>
			<td>Dried over 4&#197; sieves</td>
		</tr>
		<tr>
			<td>Trimethylindium, 98%</td>
			<td>Strem</td>
			<td>49-2010</td>
			<td>Heat sensitive, moisture sensitive</td>
		</tr>
		<tr>
			<td>Tris(trimethylsilyl)phosphine</td>
			<td>Ref #31, 32</td>
			<td></td>
			<td>Pyrophoric</td>
		</tr>
		<tr>
			<td>Ultrathin Carbon Film on Lacey Carbon Support Film, 400 mesh, Copper</td>
			<td>Ted Pella Inc.</td>
			<td>1824</td>
			<td></td>
		</tr>
		<tr>
			<td>Vacuum gauge 1-STA 115VAC 60Hz</td>
			<td>Fisher Chemical</td>
			<td>11 278</td>
			<td></td>
		</tr>
		<tr>
			<td>Vacuum pump 115VAC 60Hz</td>
			<td>Fisher Chemical</td>
			<td>01 096</td>
			<td></td>
		</tr>
		<tr>
			<td>1-Octadecene (ODE), 90%</td>
			<td>Sigma Aldrich</td>
			<td>O806</td>
			<td>Technical grade, distilled and dried over 4&#197; sieves</td>
		</tr>
	</tbody>
</table>

synthesis of in37p20(o2cr)51 clusters and their conversion to inp quantum dots

This text presents a method for the synthesis of In37P20(O2C14H27)51 clusters and their conversion to indium phosphide quantum dots. The In37P20(O2CR)51 clusters have been observed as intermediates in the synthesis of InP quantum dots from molecular precursors (In(O2CR)3, HO2CR, and P(SiMe3)3) and may be isolated as a pure reagent for subsequent study and use as a single-source precursor. These clusters readily convert to crystalline and relatively monodisperse samples of quasi-spherical InP quantum dots when subjected to thermolysis conditions in the absence of additional precursors above 200 &#176;C. The optical properties, morphology, and structure of both the clusters and quantum dots are confirmed using UV-Vis spectroscopy, photoluminescence spectroscopy, transmission electron microscopy, and powder X-ray diffraction. The molecular symmetry of the clusters is additionally confirmed by solution-phase 31P NMR spectroscopy. This protocol demonstrates the preparation and isolation of atomically-precise InP clusters, and their reliable and scalable conversion to InP QDs.

InP clusters and quantum dots are characterized by UV-Vis absorption and PL spectroscopy, XRD, TEM, and NMR spectroscopy. For the InP clusters, an asymmetric absorption feature is observed, with a peak maximum at 386 nm (Figure 1a). Despite the true monodispersity of the sample, this lowest energy peak exhibits a broad linewidth, which narrows upon decrease in temperature. This has been attributed to a set of discrete electronic transitions that are specific to the vibrational motions of the low-symmetry nanocluster lattice17. No appreciable PL QY is observed for clusters at 298 K despite the lack of obvious trap states that would arise from undercoordinated indium or phosphorus ions.
The non-stoichiometric, In-rich cluster (where In is present in a 1.85:1 ratio relative to phosphorus) results in a structure that corresponds with neither the zinc blende nor the wurzite XRD patterns of bulk InP (Figure 1b). Instead, the InP clusters attain a low-symmetry, pseudo-C2v structure that is best described by a set of intersecting polytwistane units25. The core diameter is in the 1-2 nm range depending on the axis from which it is viewed (Figure 1c). This low symmetry structure is reflected in the solution-phase 31P NMR spectrum of the cluster. The 31P NMR spectrum of myristate-capped InP clusters shows 11 distinct peaks (2 P atoms on the C2 axis that each give a unique peak and the remaining 18 P each have a symmetry equivalent, resulting in an additional 9 peaks) ranging from -187&#160;to -242&#160;ppm (Figure 1d)26. The broadness observed in the 31P NMR spectrum varies as a function of solvent and concentration, and purification method as has been recently described for related nanoscale systems27.
The optical spectra of InP QDs synthesized from clusters using the method described here display a lowest energy excitonic transition (LEET) at 564 nm and the corresponding PL emission peak at 598 nm with a full width at half maximum of 52 nm and trap emission evident at redder wavelengths (Figure 2a). It is worth noting that while the two synthetic methods (heat-up and hot-injection) yield InP QDs of comparable optical quality, the hot injection method typically leads to a sample with higher monodispersity due to the rapid nucleation at elevated temperature13. The typically low PL quantum yields obtained directly from the synthesis without further surface treatment (shelling, F- etching, or Lewis acid coordination) are hypothesized to result from a mixture of hole and electron traps present at the surface of these nanocrystals18,28.&#160;The XRD pattern of the resultant InP QDs confirms the zinc blende phase (Figure 2b). Peak broadening in the XRD data occurs due to the finite size of the highly crystalline structures, which in the case of InP QDs is 3.1 nm +/- 0.5 nm in diameter (Figure 2c, a size histogram can be found in ref. 13).
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/59425/59425fig1v2.jpg" /> 
Figure 1. Representative characterization data for InP clusters. (A) UV-Vis spectrum of InP clusters. (B) XRD pattern for purified InP clusters showing deviation from the expected bulk zinc blende (black trace) and wurtzite (grey trace) InP pattern. (C) TEM image of isolated InP clusters. (D) 31P NMR spectrum of InP clusters collected at 202 MHz in C6D6 at 298 K. <a href="https://jove.unicartagenaproxy.elogim.com/files/ftp_upload/59425/59425fig1v2large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/59425/59425fig2.jpg" /> 
Figure 2. Representative characterization data for InP quantum dots prepared from InP clusters. (A) UV-Vis (solid) and PL (dotted) spectra of InP QDs prepared from myristate-capped InP clusters using the hot-injection protocol. (B) XRD pattern of purified InP QDs showing agreement with the bulk zinc blende InP pattern. (C) TEM images of InP QDs grown from clusters using the hot-injection protocol. <a href="https://jove.unicartagenaproxy.elogim.com/files/ftp_upload/59425/59425fig2large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>

Watch this Scientific Journal Video about Synthesis of In37P20O2CR51 Clusters and Their Conversion to InP Quantum Dots at JoVE.com

Synthesis of In37P20O2CR51 Clusters and Their Conversion to InP Quantum Dots

A protocol for the synthesis of In37P20(O2C14H27)51 clusters and their conversion to indium phosphide quantum dots is presented.

Synthesis of In37P20(O2CR)51 Clusters and Their Conversion to InP Quantum Dots

This text presents a method for the synthesis of In37P20(O2C14H27)51 clusters and their conversion to indium phosphide quantum dots. The In37P20(O2CR)51 ...

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9.6K Views.  University of Washington. A protocol for the synthesis of In37P20(O2C14H27)51 clusters and their conversion to indium phosphide quantum dots is presented.

Video: Synthesis of In37P20O2CR51 Clusters and Their Conversion to InP Quantum Dots

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand.

This protocol describes the use of amide coupling reactions of isonicotinic acid and diaminoalkanes to form bridging ligands suitable for use in the synthesis of multinuclear platinum complexes, which combine aspects of the anticancer drugs BBR3464 and picoplatin.

Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. ...

Synthesis of Non-uniformly Pr-doped SrTiO3 Ceramics and Their Thermoelectric Properties

We demonstrate a novel synthesis strategy for the preparation of Pr-doped SrTiO3 ceramics via a combination of solid state reaction and spark plasma sintering techniques. Polycrystalline ceramics possessing a unique morphology can be achieved by optimizing the process parameters, particularly spark plasma sintering heating rate. The phase and morphology of the synthesized ceramics were investigated in detail using X-ray diffraction, scanning electron microcopy and energy-dispersive X-ray spectroscopy. It was observed that the grains of these bulk Pr-doped SrTiO3 ceramics were enhanced with Pr-rich grain boundaries. Electronic and thermal transport properties were also investigated as a function of temperature and doping concentration. Such a microstructure was found to give rise to improved thermoelectric properties. Specifically, it resulted in a significant improvement in carrier mobility and the thermoelectric power factor. Simultaneously, it also led to a marked reduction in the thermal conductivity. As a result, a significant improvement (> 30%) in the thermoelectric figure of merit was achieved for the whole temperature range over all previously reported maximum values for SrTiO3-based ceramics. This synthesis demonstrates the steps for the preparation of bulk polycrystalline ceramics of non-uniformly Pr-doped SrTiO3.

Synthesis of Non-uniformly Pr-doped SrTiO3 Ceramics and Their Thermoelectric Properties

A protocol for the synthesis and processing of polycrystalline SrTiO3 ceramics doped non-uniformly with Pr is presented along with the investigation of their thermoelectric properties.

We demonstrate a novel synthesis strategy for the preparation of Pr-doped SrTiO3 ceramics via a combination of solid state reaction and spark plasma ...

A Simple Method for the Size Controlled Synthesis of Stable Oligomeric Clusters of Gold Nanoparticles under Ambient Conditions

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like oligomeric clusters of these yellow nanoparticles of narrow size distribution are synthesized under ambient conditions via two methods. The delay-time method controls the number of subunits in the oligoclusters by varying the time between the addition of HAuCl4 to alkaline solution and the subsequent addition of reducing agent, NaSCN. The yellow oligoclusters produced range in size from ~3 to ~25 nm. This size range can be further extended by an add-on method utilizing hydroxylated gold chloride (Na+[Au(OH4-x)Clx]-) to auto-catalytically increase the number of subunits in the as-synthesized oligocluster nanoparticles, providing a total range of 3 nm to 70 nm. The crude oligocluster preparations display narrow size distributions and do not require further fractionation for most purposes. The oligoclusters formed can be concentrated &#62;300 fold without aggregation and the crude reaction mixtures remain stable for weeks without further processing. Because these oligomeric clusters can be concentrated before derivatization they allow expensive derivatizing agents to be used economically. In addition, we present two models by which predictions of particle size can be made with great accuracy.

We describe a simple method for producing highly stable oligomeric clusters of gold nanoparticles via the reduction of chloroauric acid (HAuCl4) with sodium thiocyanate (NaSCN). The oligoclusters have a narrow size distribution and can be produced with a wide range of sizes and surface coats.

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like ...

Synthesis of Cd-free InP/ZnS Quantum Dots Suitable for Biomedical Applications

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, quantum dots should be highly fluorescent and small/monodisperse in size. While commonly used cadmium-based quantum dots possess these qualities, they are potentially toxic due to the possible release of Cd2+ ions through nanoparticle degradation. Indium-based quantum dots, specifically InP/ZnS, have recently been explored as a viable alternative to cadmium-based quantum dots due to their relatively similar fluorescence characteristics and size. The synthesis presented here uses standard hot-injection techniques for effective nanoparticle growth; however, nanoparticle properties such as size, emission wavelength, and emission intensity can drastically change due to small changes in the reaction conditions. Therefore, reaction conditions such temperature, reaction duration, and precursor concentration should be maintained precisely to yield reproducible products. Because quantum dots are not inherently soluble in aqueous solutions, they must also undergo surface modification to impart solubility in water. In this protocol, an amphiphilic polymer is used to interact with both hydrophobic ligands on the quantum dot surface and bulk solvent water molecules. Here, a detailed protocol is provided for the synthesis of highly fluorescent InP/ZnS quantum dots that are suitable for use in biomedical applications.

In this protocol, the synthesis of Cd-free InP/ZnS quantum dots (QDs) is detailed. InP-based QDs are gaining popularity due to the toxicity of Cd2+ ions that may be released through nanoparticle degradation. After synthesis, QDs are solubilized in water using an amphiphilic polymer for use in biomedical applications.

Fluorescent nanocrystals, specifically quantum dots, have been a useful tool for many biomedical applications. For successful use in biological systems, ...

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single molecule level. An electrostatic self-assembly and covalent fixation (ESA-CF) process is used for the synthesis of the cyclic poly(tetrahydrofuran) (poly(THF)). The diffusive motion of individual cyclic polymer chains in a melt state is visualized using single molecule fluorescence imaging by incorporating a fluorophore unit in the cyclic chains. The diffusive motion of the chains is quantitatively characterized by means of a combination of mean-squared displacement (MSD) analysis and a cumulative distribution function (CDF) analysis. The cyclic polymer exhibits multiple-mode diffusion which is distinct from its linear counterpart. The results demonstrate that the diffusional heterogeneity of polymers that is often hidden behind ensemble averaging can be revealed by the efficient synthesis of the cyclic polymers using the ESA-CF process and the quantitative analysis of the diffusive motion at the single molecule level using the MSD and CDF analyses.

A protocol for the synthesis and characterization of diffusive motion of cyclic polymers at the single molecule level is presented.

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single ...

Fabrication and Testing of Photonic Thermometers

In recent years, a push for developing novel silicon photonic devices for telecommunications has generated a vast knowledge base that is now being leveraged for developing sophisticated photonic sensors. Silicon photonic sensors seek to exploit the strong confinement of light in nano-waveguides to transduce changes in physical state to changes in resonance frequency. In the case of thermometry, the thermo-optic coefficient, i.e., changes in refractive index due to temperature, causes the resonant frequency of the photonic device such as a Bragg grating to drift with temperature. We are developing a suite of photonic devices that leverage recent advances in telecom compatible light sources to fabricate cost-effective photonic temperature sensors, which can be deployed in a wide variety of settings ranging from controlled laboratory conditions, to the noisy environment of a factory floor or a residence. In this manuscript, we detail our protocol for the fabrication and testing of photonic thermometers.

We describe the process of fabrication and testing of photonic thermometers.

In recent years, a push for developing novel silicon photonic devices for telecommunications has generated a vast knowledge base that is now being ...

One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate glycosyl donor. Following azido-nitration of a glycal, the product 2-azido-1-nitrate ester can be hydrolyzed under microwave-assisted irradiation. This transformation is usually achieved using strongly nucleophilic reagents and extended reaction times. Microwave irradiation induces hydrolysis, in the absence of reagents, with short reaction times. Following denitration, the intermediate anomeric alcohol is converted, in the same pot, to the corresponding 2-azido-1-trichloroacetimidate.

A 2-azido-1-nitrate-ester can be converted to the corresponding 2-azido-1-trichloroacetimidate in a one-pot procedure. The goal of the manuscript is to demonstrate utility of the microwave reactor in carbohydrate synthesis.

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate ...

Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy

Water/solid interfaces are ubiquitous and play a key role in many environmental, biophysical, and technological processes. Resolving the internal structure and probing the hydrogen-bond (H-bond) dynamics of the water molecules adsorbed on solid surfaces are fundamental issues of water science, which remains a great challenge owing to the light mass and small size of hydrogen. Scanning tunneling microscopy (STM) is a promising tool for attacking these problems, thanks to its capabilities of sub-&#197;ngstr&#246;m spatial resolution, single-bond vibrational sensitivity, and atomic/molecular manipulation. The designed experimental system consists of a Cl-terminated tip and a sample fabricated by dosing water molecules in situ onto the Au(111)-supported NaCl(001) surfaces. The insulating NaCl films electronically decouple the water from the metal substrates, so the intrinsic frontier orbitals of water molecules are preserved. The Cl-tip facilitates the manipulation of the single water molecules, as well as gating the orbitals of water to the proximity of Fermi level (EF) via tip-water coupling. This paper outlines the detailed methods of submolecular resolution imaging, molecular/atomic manipulation, and single-bond vibrational spectroscopy of interfacial water. These studies open up a new route for investigating the H-bonded systems at the atomic scale.

Here, we present a protocol to investigate the structure and dynamics of interfacial water at the atomic scale, in terms of submolecular resolution imaging, molecular manipulation, and single-bond vibrational spectroscopy.

Water/solid interfaces are ubiquitous and play a key role in many environmental, biophysical, and technological processes. Resolving the internal ...

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles

Bicyclic aziridinium ions were generated by the removal of an appropriate leaving group through internal nucleophilic attack by nitrogen atom in the aziridine ring. The utility of bicyclic aziridinium ions, specifically 1-azoniabicyclo[3.1.0]hexane and 1-azoniabicyclo[4.1.0]heptane tosylate highlighted in the aziridine ring openings by the nucleophile with the release of the ring strain to yield the corresponding ring-expanded azaheterocycles such as pyrrolidine, piperidine and azepane with diverse substituents on the ring in regio- and stereospecific manner. Herein, we report a simple and convenient method for the preparation of the stable 1-azabicyclo[4.1.0]heptane tosylate followed by selective ring opening via a nucleophilic attack either at the bridge or at the bridgehead carbon to yield piperidine and azepane rings, respectively. This synthetic strategy allowed us to prepare biologically active natural products containing piperidine and azepane motif including sedamine, allosedamine, fagomine and balanol in highly efficient manner.

Bicyclic aziridinium ions such as 1-azoniabicyclo[4.1.0]heptane tosylate were generated from 2-[4-tolenesulfonyloxybutyl]aziridine, which was utilized for the preparation of substituted piperidines and azepanes via regio- and stereospecific ring-expansion with various nucleophiles. This highly efficient protocol allowed us to prepare diverse azaheterocycles including natural products such as fagomine, febrifugine analogue and balanol.

Bicyclic aziridinium ions were generated by the removal of an appropriate leaving group through internal nucleophilic attack by nitrogen atom in the ...

Obtention of Giant Unilamellar Hybrid Vesicles by Electroformation and Measurement of their Mechanical Properties by Micropipette Aspiration

Giant vesicles obtained from phospholipids and copolymers can be exploited in different applications: controlled and targeted drug delivery, biomolecular recognition within biosensors for diagnosis, functional membranes for artificial cells, and development of bioinspired micro/nano-reactors. In all of these applications, the characterization of their membrane properties is of fundamental importance. Among existing characterization techniques, micropipette aspiration, pioneered by E. Evans, allows the measurement of mechanical properties of the membrane such as area compressibility modulus, bending modulus and lysis stress and strain. Here, we present all the methodologies and detailed procedures to obtain giant vesicles from the thin film of a lipid or copolymer (or both), the manufacturing and surface treatment of micropipettes, and the aspiration procedure leading to the measurement of all the parameters previously mentioned.

The goal of the protocol is to reliably measure membrane mechanical properties of giant vesicles by micropipette aspiration.

Giant vesicles obtained from phospholipids and copolymers can be exploited in different applications: controlled and targeted drug delivery, biomolecular ...

Synthesis of In₃₇P₂₀(O₂CR)₅₁ Clusters and Their Conversion to InP Quantum Dots

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