M4Ag44 (p-mba) 30-4 molecular nanoparticles

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1 The University of Toledo The University of Toledo Digital Repository Theses and Dissertations 2014 M4Ag44 (p-mba) 30-4 molecular nanoparticles Brian E. Conn University of Toledo Follow this and additional works at: Recommended Citation Conn, Brian E., "M4Ag44 (p-mba) 30-4 molecular nanoparticles" (2014). Theses and Dissertations. Paper This Thesis is brought to you for free and open access by The University of Toledo Digital Repository. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of The University of Toledo Digital Repository. For more information, please see the repository's About page.

2 A Master s Thesis Titled M 4 Ag 44 (p-mba) 30 Molecular Nanoparticles by Brian E. Conn Submitted to the Graduate Faculty as partial fulfillment of the requirements for The Master of Science Degree in Chemistry Dr. Terry Bigioni, Committee Chair Dr. Wendell P. Griffith, Committee Member Dr. Dragon Isailovic, Committee Member Dr. Patricia R. Komuniecki Dean of College of Graduate Studies The University of Toledo August 2014

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4 An abstract of Ag 44 (p-mba) 30-4 Molecular Nanoparticles by Brian E. Conn Submitted to the Graduate Faculty as partial fulfillment of the requirements for The Master of Science Degree in Chemistry The University of Toledo August 2014 In recent years, molecular nanoparticles have attracted much attention due to their unique physical, optical, and electronic properties. The properties of molecular nanoparticles are shown to deviate from their larger bulk counterparts, due to quantum confinement effects and large surface-to-volume ratios. As the size of the nanoparticle shrinks to a cluster of metal atoms (<3 nm in diameter), there is an emergence of a HOMO-LUMO band gap, which is not present in transitional d-block metals. The HOMO-LUMO band gap gives rise to discrete electronic states, leading to new chemical and physical properties. Molecular nanoparticles have had a substantial impact across a diverse range of fields, including catalysis, sensing, photochemistry, optoelectronic, energy conversion, and medicine. Currently many of the synthetic procedures for molecular nanoparticles require low temperatures, long incubation times, multistep purification and hazardous reagents that produce low yields and polydisperse molecular nanoparticles with poor stability. iii

5 Although silver has very desirable physical properties, good relative abundance and low cost, gold molecular nanoparticles have been widely favored owing to their proved stability and ease of use. Unlike gold, silver is notorious for its susceptibility to oxidation, i.e., tarnishing, which has limited the development of silver-based nanotechnologies. Despite two decades of synthetic efforts, silver molecular nanoparticles that are inert or have long-term stability have remained unrealized. Herein we report a simple synthetic protocol for producing ultrastable M 4 Ag 44 (p-mba) 30 nanoparticles as a single-sized molecular product and in exceptionally large quantities. The stability, purity, and yield are substantially better than other metal nanoparticles, including gold, due to several stabilization mechanisms. Also, reported are the structural and mechanical properties of extended crystalline solids of Na 4 Ag 44 (p-mba) 30 from large-scale quantum-mechanical simulations based on the atomically-precise X-ray measured structure. Calculations show that cohesion is derived from hydrogen bonds between bundled p-mba ligands and that the superlattice s mechanical response to hydrostatic compression is characterized by a molecular-solidlike bulk modulus B 0 = 16.7 GPa, exhibiting anomalous pressure softening and a compression-induced transition to a soft-solid phase. Such a transition involves ligand flexure, which causes gear-like correlated chiral rotation of the nanoparticles. iv

6 Acknowledgements During the time I spent completing the requirements for my master of chemistry, many professors, staff workers, and students have helped me along the way. I would like to acknowledge the people that have helped me obtain my master of chemistry. First and foremost, I would like to thank my research advisor Dr. Terry P. Bigioni whose guidance allowed me to become a successful graduate student. During my studies, Dr. Bigioni showed me what is necessary to be a competent and productive research scientist through mentorship and scientific discussion. I would like to also extend my deepest gratitude to my committee members Drs. Wendell Griffith, and Dragan Isailovic. I want to give thanks to Dr. K. Kirschbaum, Dr. P. Burckel, Y. Kim, and L. Hanson for all their help using the I-Center and interpreting the collected data. I would like to acknowledge Anthony Kaminski for all his help in the stockroom. I would like to thank the University of Toledo Chemistry Department for allowing me the opportunity to purse a higher education. Lastly, I would like to give thanks to all my friends, present and past lab members for all their support. I would like to give an extra special thanks to my lab mentor, Anil Desireddy for all his advice and words of encouragement. Also, would like to thank Brian Ashenfelter, Charak Joshi, and Brad Monahan for all the insightful laboratory discussions. Most importantly, I would like to thank my mother Trish, father Fred, older brother David and the rest of my family members for their years of patience and love. v

7 Table of Contents Abstract.. iii Acknowledgements..v Table of Contents...vi List of Tables ix List of Figures. x List of Abbreviations...xv 1 Introduction Small is Different Electronics Configurations of Nanoclusters Molecular Nanoclusters References 10 2 Ultrastable silver nanoparticles Ultrastable silver nanoparticles Methods Summary Synthetic Methods X-ray Crystallography Computational Methods References 29 3 M 4 Ag 44 p-mba 30 Molecular Nanoparticles...33 vi

8 3.1 Introductions Experimental Chemicals Synthesis Electrospray Ionization Mass Spectrometry (ESI-MS) Optical Measurements NMR Stability Measurments Results and Discussion Synthesis Coordinating Solvent Stability and Seeding Decay References 52 4 Silver nanoparticle superlattice 4.1 Hydrogen bonded structure and mechanical chiral response of a silver nanoparticle superlattice Methods Computational Methods References 68 5 Conclusion.73 vii

9 Appendix A..76 Appendix B References 115 viii

10 List of Tables A1 A2 B1 Radial distances from the single crystal of Na 4 Ag 44 (p-mba) Interatomic distances from the single crystal Na 4 Ag 44 (p-mba) Average and standard deviations( in parenthesis) of the radial distances of the metals core atoms organized in shells in the Na 4 Ag 44 (p-mba) 30 nanoparticle..100 ix

11 List of Figures 1-1 (a) The mass spectrum of the sodium clusters in the gas phase with N = (b) The energy levels of the delocalize orbitals of a gas phase sodium cluster with N = A series of gold thiolated molecular nanoparticles separated by polyacrylamide gel electrophoresis (PAGE), and gold content was determined by electrospray ionization mass spectroscopy Ag:SG and Au:SG bands from the same PAGE gel, using concentrations of 15 and 30 mg/ml, respectively. The number of atoms in each Au:SG band is indicated UV/Vis absorption spectra of Ag 44 (SR) molecular nanoparticle synthesis with different aryl-thiol ligands Absorption spectrum of the M 4 Ag 44 (p-mba) 30 raw product solution (red line) synthesized in the presence of seed M 4 Ag 44 (p-mba) 30 clusters (open circles). Inset: 140 grams of M 4 Ag 44 (p-mba) 30 clusters pictured with two 1 oz. silver coins for scale. The dish is 18 cm in diameter Electrospray-ionization mass spectra (ESI-MS) of the final product without size separation shows that only one species is present X-ray crystal structure obtained from a Na 4 Ag 44 (p-mba) 30 crystal.23 x

12 2-4 Projected densities of states (PDOS) and orbital images M 4 Ag 44 (p-mba) 30 nanoparticles shown in solid and in solution forms. The dice represent the four Platonic solids that can be found in the structure M 4 Ag 44 (p-mba) 30 absorbance. Molar absorptivity of M 4 Ag 44 (p-mba) 30 nanoparticles in DMF solution. Inset shows the absorbance as a function of energy ESI-MS of M 4 Ag 44 (p-mba) 30. (A) Raw product, containing excess alkali metal counterions. (B) Fully protonated final product M 4 Ag 44 (p-mba) 30 crystal structure. Space-filling view of the structure down a 3-fold axis. Ligand bundling creates gaps that leave the Ag atoms in the mounts 3-5 H1 NMR and NOSY of M 4 Ag 44 (p-mba) 30. (left-a) Aromatic protons are shown for nanoparticles in DMF. (right-b) NOSY shows coupling between bridging ligands and ligands at the base of the mounts, as well as coupling between ligands at the base of the mounts.(blue) exposed to chemical attack. Color scheme: grey C; orange O; yellow S; blue Ag in mounts; green Ag in decahedral outer core shell Spectral evolution during M 4 Ag 44 (p-mba) 30 synthesis. Silver thiolates at 0 min are reduced to immediately form M 4 Ag 44 (p-mba) 30 nanoparticles, with characteristic spectra observed beginning after 1 min and persisting for the entire reaction (~1 h) 47 xi

13 3-7 Temporal stability of M 4 Ag 44 (p-mba) 30 in DMSO. Aged DMSO solutions of M 4 Ag 44 (p-mba) 30 retain their characteristic spectra, indicating that no other nanoparticle species were produced. Absorbances were not rescaled Polymerization of M 4 Ag 44 (p-mba) 30. (left) Dissolving the product in neat water leads to the formation of plasmonic Ag nanoparticles. (right) Electron micrograph of the resultant plasmonic nanoparticles Ag44(p-MBA)30.Na4 superlattice structure Superlattice compression, and rotational structural transition Intra- and inter- nanoparticle distances and angles induced by the applied compression (V/V0) of the superlattice.64 A1. Gel electrophoresis of Ag clusters run on the same gel. (A) Glutathione-capped Ag clusters, with Ag 32 (SG) 19 indicated. (B) p-mba-capped Ag clusters, with three major bands observed. (C) Absorption spectra of the three prominent gel bands, offset for clarity..80 A2. (a) ESI-MS of the final product without size separation shows that only one species is present, with other peaks accounted to different charge states, fragments and non-specific dimerization. (b) Isolated Ag 44 L 4 30 ions spontaneously fragment into Ag 43 L 3 28 and AgL 2 when desolvated, where L is p-mba. Inset: the experimental data (black) were fit (blue) using a simulation of the Ag 44 L 4 30 ion isotopic distribution (red bars) and that of its Na salt (green bars) 82 A3. Tandem mass spectrometry of Ag 44 L ions 83 xii

14 A4. (A) Gel electrophoresis of Au:SG clusters synthesized with and without Au 25 SG 18 cluster seeds. Synthesis with seeds (middle) shows that the Au 25 SG 18 clusters reacted to form larger clusters. Adding seeds after the synthesis shows the result expected had the Au 25 SG 18 clusters been inert. (B) Comparison of M 4 Ag 44 (p-mba) 30 and Au 25 SG 18 solution ambient stability, with linear fits shown in red. Open symbols for Au indicate that the spectra contain other species...87 A5. Optical micrographs of typical crystals of M 4 Ag 44 (pmba) 30 clusters using (left) episcopic and (right) diascopic illumination 89 A6. Radial atomic distance distribution, with respect to the center of the x-ray determined structure of the Ag 44 (pmba) cluster. The radial distances of the 6 outer sulfur atoms is given in black (centered about 8.2 Å). A Gaussian convolution with σ = 0.03 A was used..92 B1(a) Optimal structure of the Na 4 Ag 44 (p-mba) 30 nanoparticle showing silver core and p-mba ligands..99 B1(b) Two views (a and b) of the p-mba ligand-ligand binding between two neighboring silver nanoparticles, both located in the same layer of the superlattice B1(c) Two views (a and b) of the p-mba ligand-ligand binding between two neighboring silver nanoparticles, located in neighboring layers of the superlattice..102 xiii

15 B2(a) Intralayer and interlayer NP rotations. Configuration of two neighboring nanoparticles, both located in the same layer of the superlattice 108 B2(b) Intralayer and interlayer NP rotations. Configuration of two neighboring nanoparticles, located in neighboring layers of the superlattice, denoted as α and β 109 B2(c,d) Configurations of the superlattice viewed normal to the (a,b) [or (x,y) plane] plane (as in Figure B2(a). The configuration in (C) corresponds to V/V 0 = 1.0 and the one in (d) corresponds to the end of the compression process at V/V 0 = B3 Torsion angles plotted versus the compression parameter V/V0.112 B4 Compression-induced changes in the structure of the Na 4 Ag 44 (p-mba) 30 nanoparticle in the superlattice 113 xiv

16 List of Abbreviations APS...Ammonium Persulfate CTAB...Cetyl Trimethyl Ammonium Bromide DCTB...Trans-2-[3-(4-tetra-butylphenyl)-2-methyl-2-propenylidene] malononitrile DHB...2,4 Dihydroxy Benzoicacid DLVO...Derjaguin and Landau, Verwey and Overbeek DMF...Dimethyl Formammide DMSO...Dimethyl Sulfoxide EDS...Energy Dispersive Spectroscopy ESI-MS...Electrospray Ionization Mass Spectrometry FFT...Fast Fourier Transformation GGA...Generalized Gradient Approximation GSH...Glutathione HDMS...High Definition Mass Spectrometer HOMO...Highest Occupied Molecular Orbital IBANs...Intensely and Broadly Absorbing Nanoparticles ICP-OES...Inductively Coupled Plasma Optical Emission Spectrometry xv

17 LDI...Laser Desorption/Ionization LUMO...Lowest Unoccupied Molecular Orbital MALDI...Matrix Assisted Laser Desorption/Ionization MEF...Metal Enhanced Fluorescence MS...Mass Spectrometry PAGE...Polyacrylamide Gel Electrophoresis PDOS...Projected Density of States p-mba...para-meracapto Benzoic Acid SC-XRD...Single Crystal X-ray Diffraction SDS...Sodium Dodecyl Sulfate SEM...Scanning Electron Microscope SERS...Surface-Enhanced Raman Scattering STEM...Scanning Transmission Electron Microscope TDDFT...Time-Dependent Density Functional Theory TEM...Transmission Electron Microscope TEMED...Tetramethylethylenediamine THAM...Tris(hydroxymethyl) Aminomethane THF...Tetrahydro Furan TMAD...Tetramethylammonium decanoate TOAB...Tetraoctylammoniumbromide TOF...Time-of-Flight VASP-DFT...Vienna Ab-initio Simulation Package-Density Functional Theory xvi

18 Chapter 1 Introduction 1.1 Small is Different Molecular nanoparticles are a collection of atoms in a finite aggregation that range between atoms. 1-3 In the nanometer s size regime, the properties of bulk materials transition into atoms and molecules, and it is during this transition that nanoclusters may yield divergently different properties from their bulk counterpart. 1, 4 The phenomenon of quantum confinement plays a dominant role in the emergence of unique size-dependent physical and chemical properties of a molecular nanoparticle when it is in the size range of <3 nm. 1,2,3,5 The unique size-dependent properties of molecular nanoparticles allow them to have a substantial impact across a diverse range of fields, including catalysis, 6 sensing, 7 photochemistry, 8 optoelectronics, 9,10 energy conversion, 11 and medicine. 12 The characteristics of the nanoclusters unique properties arise from their large surface-to-volume ratios, 1,2,4 quantum confinement, 1-5,13 and structural and energetic size effects. 1,2,3,13 As the volume of the molecular nanoparticles decreases, the ratio of the surface area-to-volume increases. 1,2,4 This increased surface area-to-volume means the constituent surface atoms have fewer nearest neighbors, and therefore, fewer satisfied bonds. 4 These unsatisfied bonds require additional energy to maintain the bond distance 1

19 between the surface atoms and the atoms of the underlying layer. 4 This added energy proves to have a significant role in determining the overall stability, the structure, and energetics of the nanoparticle, and rationalizes why the addition or removal of one atom may have a remarkable altering effect to the nanoparticle s integrity. 1 The small sizes of molecular nanoparticles can generate multiple size effects that will dictate their chemical, physical, and electrical properties, and subsequently allow for these properties to deviate from those of the bulk materials. 1-6, The unique properties of molecular nanoparticles may be attributed to the quantum confinement of their electrons The quantum confinement of the electrons yield quantized energy levels that generate a highest occupied molecular orbital and a lowest unoccupied molecular orbital (HOMO-LUMO) band gap Possession of a HOMO-LUMO gap is common for molecules, but for transition d-block metals it is considered an anomaly. When metals are reduced to just a few atoms in diameter, their continuous conduction band transforms into discrete energy levels The physical and chemical properties of molecular nanoparticles are strongly dependent on the electronic transition between the HOMO and LUMO gap 14, 15. Therefore, as the molecular nanoparticles becomes smaller (or larger) the electronic transitions between its HOMO-LUMO gap are altered, and so are the chemical and physical properties of the nanoparticle. Once the molecular nanoparticle exceeds a certain size limit, further enlargement of the cluster proves to have minimal effect on its properties. However, because shrinking a material into the nanometer size range produces new and unique properties this validates the statement that small is different. 3,17,18 2

20 electronic shell closings since large HOMO-LUMO gaps make it more difficult for 1.2 Electronics Configurations of Molecular Nanoparticles Elements with noble gas configurations are chemically inert due to their electronic shells being closed. 19 The stability of molecular nanoparticles are strongly dependent on their electronic configurations. Knight et al. discovered when sodium spectrometry (ESI-MS) If crystallized, their total structure can even be determined by cluster are formed in the gas phase there is mass distribution pattern. 20 As shown in single-crystal X-ray diffraction (sc-xrd). 4,11-14 Figure 1-1 (a), the sodium clusters mass abundances were predominately higher for Magic-number theory was developed to explain the stability of certain cluster clusters with N = 8, 20, 40, 58 and 92, where N is the number of sodium atoms in the sizes in a gas phase cluster beam. 5,15-18 Cluster stability was found to depend on two cluster. 20, 21 The relative abundances of the sodium clusters can be associated with their things: (1) electronic shell closings and (2) geometric shell closings. 5,6,18-20 This magicnumber theory has now been successfully applied to explain the anomalous stability of relative stability Sodium cluster with N = 8, 20, 40, 58 and 92 are shown to have the higher stability, because they have a complete electronic shell configuration, as shown in thiolate-passivated gold clusters in the condensed phase. 5 Figure 1-1 Sodium (b) of N has = 40. one free When 3s electron electronic and shells is known are filled, to form they produce abundant a potential gas-phase energy clusters minimum of specific that numbers lowers the of free atoms, energy, as shown which in supplies Figure additional 1-1a. 19 This stability is due to to the the molecular stability created nanoparticles. by electronically 19,22 closed shell, as shown in Figure 1-1b. 19 Figure Figure 1-1: 1-1: (a) The Sodium mass has spectrum one free of 3s the electron sodium and clusters is known in the to gas form phase abundant with N gasphase = (b) The clusters energy of levels specific of the numbers delocalize of atoms orbitals (a) of Gas a gas phase phase abundance sodium cluster of sodium with N clusters = of different size (b) Effective potential of Na Reprinted with permission from reference 20. Copyright 40 cluster as function of radius American Physics Society. Reprinted with permission from reference 19 (copyright 1993, APS) 1.2 Electronic structure theory (electronic shell closing model) 3 The stability of small Au magic-number clusters has been attributed to

21 In the gas phase there are limited cluster-to-cluster interactions, which are assumed in the ideal gas law. The limited cluster-to-cluster interactions limit the aggregation process of molecular nanoparticles, but the cluster-to-cluster interactions are not completely impeded in the gas phase. This is why even though N = 8, 20, 40, 58 and 92 sodium cluster have the highest stability; they are not the only sodium clusters present in the gas phase. In contrast to the gas phase, the condensed phase of clusters have significant cluster-to-cluster interactions. Therefore, when clusters are in the condensed phase, they must be a protected by a capping group that stabilize and prevent nanoparticles aggregation by hindering the interactions between neighboring clusters. The protecting or capping groups on clusters are called ligands, and are directly coordinated to the metal core of the cluster. 19 The ligand is usually an organic compound that attaches to the metal core of the nanoparticle by covalent bonds or as a weak Lewis base. 19 Once the ligands are coordinated to the metal cluster, they contribute to the overall electronic configuration of the cluster. 19 A theory was developed that determines the electron configuration of a cluster or molecular nanoparticles, and is analogous to atomic theory and the Aufbau rule. 19 The electrons of molecular nanoparticles behave as superatom electronic complexes rather than individual atoms. 19, 22 Superatom electronic complexes have metal atoms coordinated to localized ligands, which contributes to the overall electronic shell configuration. 19,22 Therefore, both the metal core and ligands attributed to the closing of the electron shell configuration for superatom complexes. 19 Walters et al. developed the superatom electronic theory, which predicts the chemical identity and stability of simple metal molecular nanoparticles. 19 The superatom electronic theory 4

22 accounts for the delocalized orbitals of the molecular nanoparticle, and the electric shell configuration is 1S 2 1P 6 1D 10 2S 2 1F 14 2P 6 1G The electronic shell filling rules are predicted by the equation: N* = Nν A M z Where N* is the shell- closing electron count, N is the number of metal atoms, ν A is the number of valence electrons of the metal atom, M is the number of electron withdrawing (or localizing) ligands, and z is the overall charge on the cluster Molecular Nanoparticles Nanoparticles have been used as early as in the 4 th century 23, but it wasn t until the mid 1800 s that Michael Faraday first published his discovery of colloidal gold nanoparticles. 23 Over the next century there was very little research pertaining to nanoparticles, and this was due to the limiting characterization techniques. The emergence of the high resolution microscopes, such as SEM, TEM, STM and AFM, as well as, popularized nanotechnology writings of Richard Feynman and Eric Drexler in their titled works There s plenty of room at the bottom, and Engine of creations, respectfully, led to cultivation of interest in nanoscience. The unique optical, structural, electronic, and physical properties of nanoparticles are what sustained the simulation of research in nanomaterials. 1-3,5,19,22,24,25 One of the major synthetic milestones for nanoparticles was by Brust et al., where they reported the synthesis of highly stablized thiol capped gold nanoparticles. 26 The synthesis is now referred to as the Brust-Schiffrin synthesis, and it allowed for the wide availability of gold nanoparticles for research. 26 5

23 Whetten et al. published a landmark paper in the field of molecular nanoparticles in 1996, in which they predicted, isolated, and characterized a set of gold molecular nanoparticles. 27 This paper was monumental because it showed that nanoparticles could be defined as molecular systems. The idea that nanoparticles could be viewed as molecules was a contemporary notion, because at the current time only polydisperse (i.e., plus and minus hundred of atoms) nanoparticles were observed. Having an isolated single-sized molecular nanoparticle allows for the use of molecular type characterizations techniques, such, as mass spectrometry and single crystal x-ray diffraction. The singlesize molecular nanoparticle along with molecular characterization techniques provides a pathway to study the fundamentals of nanoparticles size-dependent properties. While in the case of polydisperse nanoparticles, the assortment of different sizes would provide inconsistency when trying to accurately determine the size-dependent properties of nanoparticles. 27 To study the size dependent chemical and physical properties of molecular nanoparticles, the nanoparticles must be isolated and chemically inert. Negishi et al., were the first to report the synthesis and isolation of an all-thiol family of gold nanoparticles. 28,29 The gold molecular nanoparticles were separated by polyacrylamide gel electrophoresis (PAGE), and in Figure 1-2 the extracted gold molecular nanoparticles can be viewed in solution. 28,29 The molecular formula of each extracted gold nanoparticle was determined by electrospray ionization mass spectroscopy (ESI-MS). The work by Negishi et al. provided a great system to probe the chemical properties of a series of molecular gold nanoparticles, but Negishi et al. study didn t reveal any information about the atomic structure of a molecular nanoparticle. 28,29 6

24 Figure 1-2: A series of gold thiolated molecular nanoparticles separated by polyacrylamide gel electrophoresis (PAGE), and gold content was determined by electrospray ionization mass spectroscopy. Reprinted with permission from reference 29. Copyright 2005 American Chemical Society. It was two years after Negishi et al. published their work on all-thiol molecular gold nanoparticles that the Kornberg group successfully produced a single crystal of an all-thiol molecular gold nanoparticle with the molecular formula Au 102 (p-mba) The crystal structure of Au 102 (p-mba) 44 revealed its spherical atomic structure, with an all metal core and capped with 2D Au-SR-Au-SR-Au and Au-SR-Au staples that passivate the gold core. 30 SR represent a thiolated ligand. The electronic structure satisfies supramolecular theory by having a 58 electron closed shell. 19,30 The crystal structure of Au 25 (SR) 18, Au 38 (SR), have since been reported after the crystallization of Au 102 (p- MBA) Each of the three molecular nanoparticle crystal structures have a 13-atom icosahedron core, and ligand capped with 2D Au 3 (SR) 2 and Au 2 (SR) staples To 7

25 a Parenthese Different synthesis conditions were able to change the overall composition of the raw product but did not change the component clusters. For example, changing the solvent composition, Ag:GSH ratio, and reduction rate shifted the mass distribution toward either larger or smaller cluster sizes (see Supporting Information), while determine if the trends displayed in the family of gold molecular nanoparticles are the relative positions and colors of the PAGE bands were specific independent to only gold of nanoparticles reaction conditions. or to all metal The nanoparticles, pattern and it is colors vital that of other metal bands were always reproduced with only variations in their molecular abundance, nanoparticles strongly are explored. suggesting the molecular precision of magicnumber In recent clusters. years, there has been an effort to examine non-gold molecular The similarities between Au and Ag allow comparisons to be nanoparticles made between in regards the of finding patterns generalizable of PAGErules bands for molecular for eachnanoparticles. family of Silver clusters. Both Au and Ag contribute one free electron per atom to molecular nanoparticles have been explored to test the generality of molecular the clusters, so the same pattern of electronic shell closings as a nanoparticle function stability of theand number formation. of core Silver atoms is a less isnoble expected than gold, for each but silver metal. posses Figure 3. Op Further, the atomic sizes and alkyl thiol packing densities are almost labeled, chosen superior identical optical for and bulk antibacterial Au andproperties, Ag. 16 The and same two orders pattern of magnitude of atomic cheaper shell than were taken of c closings is therefore expected, and the charge and electrophoretic gold. Kumar et al. was the first to report the synthesis and separation of a family of silver Table 1. Salie mobility for the same size clusters should also be similar. A similar molecular pattern nanoparticles. of bands 34 isit therefore was shown expected. that the family of silver- band 2 band 6 band 9 band 13 Figure Figure 1-3: Ag:SG 2. Ag:SG and Au:SG and Au:SG bands from bands the from same the PAGE same gel, PAGE using concentrations gel, using of 15 and concentrations 30 mg/ml, respectively. of 15 and 30 The mg/ml, number respectively. of atoms in The each number Au:SG band of atoms is indicated. 34 Reprinted each with Au:SG permission band indicated. from reference Copyright 2010 American Chemical Society. The patterns of bands for Au and Ag clusters run on the same gel are shown in Figure 2. Although there is some correspondence between individual bands, it is immediately apparent that the mass distribution is quite different for the two families of clusters. This glutathione suggests were that related the to most the family stableof structures gold-glutathione may be nanoparticles different since synthesized by most abundant Au:SG and Ag:SG clusters are not necessarily the clusters, they Negishi same et al, size. but the This relationship could bewas duenot toa adirect difference comparison. in Au-S 34 In Figure and Ag-S 1-3, the PAGE chemistry, or it could indicate a need to consider new models. separations of the Ag and Au glutathione can be interpreted as similar by their individual There are also striking differences in the optical properties of Au and Ag clusters. The optical density of Ag is significantly higher than that of Au, as can be seen in Figure 2. The integrated spectrum 8 ( nm) of the raw Ag:SG mixture was almost double that of Au:SG (see Supporting Information). The absorption spectra of prepared clus in aqueous s smallest parti lost after 1 idea that smal larger HOMO the gel. In conclus of small glu properties of conditions, co clusters. Alth suggests that could be diff chemistry. A theories may Acknowle Ronning and Mishra and M

26 band overlap, but the mass distribution between the individual bands are not the same. 34 The varying mass distribution in the silver and gold glutathione nanoparticles can be rationalized by the different chemistry of the metal atoms with the organic thiol ligand, which suggest the generalized rules for gold molecular nanoparticles may not be directly applicable to silver containing molecular nanoparticles. 34 While there have been many solution-phase methods for synthesizing gold and silver molecular nanoparticles there is one synthesis that has been significantly remarkable. The synthesis by Bakr et al. was reported to yield a single-sized silver molecular nanoparticle. 23, 35,36 At the time many of the solution-phase methods produced a series of different size molecular nanoparticles (as mentioned above), but none of the syntheses yields only a single-size product. 23, 30,3-436 The silver molecular nanoparticle was classified as an intensely and broadly absorbing nanoparticle (IBAN), and its molecular formula was determined by ESI-MS to be Ag 44 (SR) ,35,36 The IBAN s spectrum can be viewed in Figure 1-4, and is categorized by its 8 distant optical peaks that span the entire visible spectrum. 23,35,36 Ag 44 (SR) was reported to be stable for 18 months in the freezer, and accredits its stability to the 18 electron count closed shell configuration. 23,36-4 The Ag 44 (SR) 30 molecular nanoparticle is a special system that needs further exploration, so a deeper understanding of why only a single size molecular nanoparticle is formed during synthesis. 9

27 Figure 1-4: UV/Vis absorption spectra of Ag 44 (SR) 30-4 molecular nanoparticle synthesis with different aryl-thiol ligands. Reprinted with permission from reference 35. Copyright 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. 1.4 References 1. Jortner, J. Cluster size effects. Atoms, Molecules and Clusters 1992, 24, Heer, W., A. The physics of simple metal clusters: experimental aspects and simple models. Reviews of Modern Physics, 1993, Barnett, R., N., Yannouleas, C., and Landman, U. Small can be different. Z. Phys. D, 1993, 26, Cao, Guozhong. Nanostructures & nanomaterials synthesis, properties & applications. Imperial College Press, London, Zhu, M., Aikens, C. M., Hollander, F.J., Schatz, G. C., Jin, R. J. Correlating the Crystal Structure of A Thiol-Protected Au 25 Cluster and Optical Properties. J. Am. Chem Soc. 2008, 130, Heiz, U., Landman, U. Nanocatalysis. Springer-Verlag, Berlin,

28 7. Anker, J.N. et al., Biosensing with plasmonic nanosensors. Nat. Mater. 2008, 7, Jin, R. et al., Controlling anisotropic nanoparticle growth through plasmon excitation. Nature. 2003, 425, Maier, S.A. et al., Plasmonics - A route to nanoscale optical devices. Adv. Mat. 2001, 13, Noginov, M.A. et al., Demonstration of a spaser-based nanolaser. Nature. 2009, 460, Atwater, H.A., Polman, A. Plasmonics for improved photovoltaic devices. Nat. Mater. 2010, 9, Arvizo, R.R., et al., Intrinsic therapeutic applications of noble metal nanoparticles: past, present and future. Chem. Soc. Rev. 2012, 41, Häkkinen, H. in Fronttier of Nanoscience. Ligand-protected Gold Nanoclusters as Superatoms - Insights from Theory and Computations, Johnston R.L., Wilcoxon J. Ed., Elsevier: Great Britian, Vol 3, p Jin, R. Quantum sized, thiolate-protected gold nanoclusters. Nanoscal. 2010, 2, Sattler, K. The Energy Gap of Clusters Nanoparticles, and Quantum Dots. In Handbook of thin film materials, Nalwa, H. S., Ed., Academic Press: San Diego, Vol. 5, p Atkins, P. W., Julio P. Physical chemistry, 9th ed., W. H. Freeman and Co: New York,

29 17. El-Sayed, M., A. Small Is Different: Shape-, Size-, and Composition-Dependent Properties of Some Colloidal Semiconductor Nanocrystals. Acc. Chem. Res., 2004, 37 (5), pp Landman, U., Luedtke, W., D. Small is different: energetic, structural, thermal and mechanical properties of passivated nanocluster aseemblies. Faraday Discuss. 2004, 125, Walter,M., Akola, J., Lopez-Acevedo, O., Jadzinsky, P. D., Calero. G., Ackerson, C. J., Whetten, R. L., Grönbeck, H., Häkkinen, H. A unified view of ligand-protected gold clusters as superatom complexes, PROC. NATL. ACAD. SCI. 2008, 105, Knight, W.D., Clemenger, K., deheer, W. A., Saunders, W. A., Chou, M. Y., Cohen, M. L. Electronic shell structure and abundances of sodium clusters Phys. Rev. Lett. 1984, Eberhardt, W. Clusters as new materials. Surface science 2002, 500, Harkness, K. M., et al. Ag 44 (SR) : a silver-thiolate superatom complex. Nanoscale 2012, 4(14), Faraday, M. Experimental relations of gold (and Other Metals) to Light. Philosophical Transactions of the Royal Society of London, 1857, 147, Whetten, R. L. et al. Crystal structures of molecular gold nanocrystal arrays. Acc. Chem. Res. 1999, 32, Templeton, A. C., Wuelfing, P. W., Murray, R. W., Monolayer-protected cluster molecules. Acc. Chem. Res. 2000, 33,

30 26. Brust, M., Walker, M., Bethell, D., Schriffin, D. J., Whyman, R. Synthesis of Thiolderivatised gold nanoparticles in a two-phase liquid-liquid system. J. Chem. So., Chem. Commu., 1994, Whetten, R., L. et al. Nanocrystal gold molecules. Adv. Mater. 1996, Negishi, Y., Takasugi, Y., Sato, S., Yao, H., Kimura, K., Tsukuda, T. Magic-numbered Au n clusters protected by glutathione monolayers (n = 18, 21, 25, 28, 32, 39): isolation and spectroscopic characterization. J. Am. Chem. Soc., 2004, 126 (21), Negishi, Y.; Nobusada, K.; Tsukuda, T. Glutathione-protected gold clusters revisited, J. Am. Chem. Soc. 2005, 127, Jadzinksy, P. D., Calero, G., Ackerson, C. J., Bushnell, D. A., Kornberg, R. D., Strucuture of a thiol monolayer-protected gold nanoparticle at 1.1 A resolution. Science. 2007, 318, Zhu, M., Aikens, C. M., Hollander, F. J., Schatz, G. C., Jin, R. Correlating the crystal strucuture of a thiol-protected Au25 cluster and optical properties. J. Am. Chem. Soc., 2008, 130 (18), Heaven, M. W., Dass, A., White, P. S., Holt, K. M., Murrary, R. W. Crystal strucuture of gold nanoparticle [N(C 8 H 17 ) 4 ][Au 25 (SCH 2 CH 2 Ph) 18 ]. J. Am. Chem. Soc., 2008, 13 (12), Qian, H., Eckenhoff, W. T., Zhu, Y., Pintauer, T., Jin, R. Total structure determination of thiolated-protected Au 38 nanoparticles. J. Am. Chem. Soc., 2010, 132 (24), Kumar, S., Bolan, M. D., Bigioni, T. P., Glutathione-stabilizd magic-numbered silver cluster compounds. J. Am. Chem. Soc. 2010,

31 35. Bakr, O. M., Amendola, V., Aikens, C. M., Wenseleers, W., Li. R., Negro, L. D., Schatz, G. C., Stellacci, F. Silver nanoparticles with broad multiband linear optical absorption. Angew. Chem. Int. Ed. 2009, 48, Pelton, M., Tang, Y., Bakr, O. M., Stellacci, F. Long-lived charged-separated states in ligand-stabilized silver clusters. J. Am. Chem. Soc. 2012, 134,

32 Chapter ULTRASTABLE SILVER NANOPARTICLES Noble metal nanoparticles have had a deep impact across a diverse range of fields, including catalysis, 1 sensing, 2 photochemistry, 3 optoelectronics, 4,5 energy conversion, 6 and medicine. 7 Although silver has very desirable physical properties, good relative abundance, and low cost, gold nanoparticles have been widely favored due to their proven stability and ease of use. Unlike gold, silver is notorious for its susceptibility to oxidation, i.e. tarnishing, which has limited the development of important silver-based nanomaterials. Despite two decades of synthetic efforts, inert or long-term stable Ag nanoparticles remain unrealized. Herein we report a simple synthetic protocol for producing ultrastable M 4 Ag 44 (p- MBA) 30 nanoparticles as a self-selecting single-sized molecular product in exceptionally large quantities, with quantitative yield, and without the need for size sorting. The stability, purity, and yield are substantially better than other metal nanoparticles, including gold, owing to an effective stabilization mechanism. The particular size and stoichiometry of the product was found to be immune to variations in synthesis parameters. The unique chemical stability and structural, electronic and optical properties are understood using *Reprinted from the Desireddy, A., Conn, B. E., Guo, J., Yoon, B., Barnett, R. N., Monahan, B. M., Kirschbaum, K., Griffith, W. P., Whetten, R. L., Landman, U., Bigioni, T. P. Ultrastable Silver Nanoparticles. Nature 501, (2013). Copyright Nature Publishing Group. 15

33 first-principles electronic structure theory based on an experimental single-crystal X-ray structure. While several structures have been determined for protected gold nanoclusters, 8-12 none has been reported to-date for silver nanoparticles. The total structure of a thiolate-protected silver nanocluster reported here uncovers the unique structure of the silver-thiolate protecting layer, consisting of Ag 2 S 5 mounts. The exceptional stability of the nanoparticle is attributed to a closed-shell 18-electron configuration with a large HOMO-LUMO gap, an ultrastable 32-silver atom excavateddodecahedral 13 core consisting of a hollow 12-Ag atom icosahedron encapsulated by a 20- Ag atom dodecahedron, and the choice of protective coordinating ligands. The facile synthesis of large quantities of pure molecular product promises to make this class of materials widely available for further research and technology development All-aromatic silver-thiolate clusters with a ~1.2 nm core diameter have been discovered only recently. 19 Electrospray-ionization mass spectrometry (ESI-MS) identified these as discrete molecular complexes, Ag 44 (SR) Complexity of preparation and handling have proven limiting, however, as these clusters shared the typical vulnerabilities of Ag nanoparticles. We have developed an entirely new approach for the preparation of ultrastable silver nanoparticles in semi-aqueous solution with an all-aromatic p-mercaptobenzoic acid (p-mba) protecting ligand shell. 8,19 With judicious choice of solvent conditions and stabilizing agents we have transformed these fragile and unstable Ag complexes into chemically inert materials with unprecedented stability. 16

34 The synthesis involves the reduction of a soluble precursor in semiaqueous solution and in the presence of alkali metal cations and a coordinating solvent. The straightforward protocol produces a pure molecular material without size separations and achieves near quantitative yield in exceedingly large quantities (see Figure 2-1 inset). The product can be dried and fully redispersed in protic, aprotic, and nonpolar solvents with no loss of material or change in chemical identity. Figure 2-1. Optical absorption and material sample. Absorption spectrum of the M 4 Ag 44 (p-mba) 30 raw product solution (red line) synthesized in the presence of seed M 4 Ag 44 (p-mba) 30 clusters (open circles). Inset: 140 grams of M 4 Ag 44 (p-mba) 30 clusters pictured with two 1 oz. silver coins for scale. The dish is 18 cm in diameter. 17

35 The absorption spectrum of the raw product is highly structured (see Figure 2-1) and identical to that of the purified material, with an onset at about 1100 nm (~ 1.1 ev). ESI-MS of the raw product (see Figure 2-2) identified several ion species that were all attributed to a single cluster size, the pure Ag 44 (p-mba) 4 30 complex (m/z 2336). The Ag 43 (p-mba) 3 28 complex (m/z 2975) was attributed to electrostatic destabilization and spontaneous fragmentation of Ag 44 (p-mba) 4 30 upon desolvation (see Appendix A). The experimental data only matched the simulated isotopic distribution for the fully protonated species (see Appendix A), therefore the entire -4 charge was carried by the silver core rather than by the carboxylates. Four alkali counterions (M) were identified by elemental analysis, giving M 4 Ag 44 (p-mba) 30 as the molecular formula. Figure 2-2. Electrospray-ionization mass spectra. ESI-MS of the final product without size separation shows that only one species is present. Peaks from m/z are fragments with -3 charge state and the broad intensity at 3500 m/z is attributed to nonspecific dimerization of fragments with -5 total charge state. (see Appendix A for further details) 18

36 The synthesis of M 4 Ag 44 (p-mba) 30 has characteristics unlike any nanoparticle preparation. Normally single-sized products are isolated by attrition, wherein the less stable sizes are either destroyed or converted into the most stable size Direct synthesis of a truly single-sized molecular product with yields >95% indicates that these clusters are more stable than any other known cluster species. Furthermore, the particular size, composition, and stoichiometry of the nanocluster product was found to be immune to changes in experimental parameters (e.g. solvent composition, reactant concentrations) for the sizesorting-free synthesis method developed and employed by us here. The profound difference between canonical nanoparticle syntheses and the present work was demonstrated by synthesizing M 4 Ag 44 (p-mba) 30 clusters in the presence of existing M 4 Ag 44 (p-mba) 30 clusters. Normally the existing nanoparticles would act as seeds and grow at the expense of new particle nucleation. 24 Instead, M 4 Ag 44 (p-mba) 30 clusters were formed with identical yield and chemical identity, with or without these seeds (Figure 2-1). Once formed, M 4 Ag 44 (p-mba) 30 clusters were extraordinarily stable and unreactive, behaving as completely inert molecules rather than as typical nanoparticles. When an analogous reaction was performed with Au 25 (SG) 18 (SG = glutathionate), the clusters were not inert but rather acted as seeds (see Appendix A). The long-term stability of solutions of M 4 Ag 44 (p-mba) 30 clusters were also superior to those of Au 25 (SG) 18 clusters. The ambient decay rates of M 4 Ag 44 (p-mba) 30 cluster solutions were ~7 times slower than those of Au 25 (SG) 18 cluster solutions (see Appendix, Figure A4B). Therefore, under both ambient (mildly oxidizing) and reducing conditions the M 4 Ag 44 (p-mba) 30 clusters proved to be more noble than even the highly stable Au 25 (SG) 18 19

37 cluster. 21 When discussing relative stabilities of protected nanoclusters caution should be exercised with regard to the ligands used and the environmental conditions (see Appendix A). Indeed, experiments in our laboratory have shown that Au 25 (p-mba) 18 is too unstable for meaningful temporal stability measurements to be made. This remarkable inertness under reducing conditions implies that the synthesis of new clusters can carry on without regard for existing clusters in the reaction vessel, giving impetus to scaling up the reaction. Indeed, it has been possible to produce 140 grams of the final M 4 Ag 44 (p-mba) 30 product from a single reaction (see Figure 2-1 inset), although kilogram-scale syntheses should be easily achievable. We note that 140 g is three orders of magnitude larger than typical nanoparticle preparations. Clues as to the origins of the extraordinary stability of M 4 Ag 44 (p-mba) 30 as well as the structure of the thiol surface layers that protect silver nanoparticles have been revealed by single-crystal x-ray diffraction. Na 4 Ag 44 (p-mba) 30 clusters were crystallized from DMF solution, with rhombus-shaped crystals forming after 1-3 days. The entire structure of the cluster was determined by single-crystal x-ray crystallography (see Appendix A), and is shown in Figs. 2-3(a,b). The crystal structure has exceptionally high symmetry, containing elements that exhibit four of the five Platonic solids. The all-silver core consists of a hollow icosahedron (Ag 12 inner core) within a dodecahedron (Ag 20 outer core), forming an Ag 32 excavateddodecahedral core with icosahedral symmetry (Figure 2-3 c,d); interestingly, a hollow core has been recently put forward theoretically for another thiol-protected Ag cluster. 25 The 20 atoms of the outer core occupy two distinct environments. Eight Ag atoms within the 20

38 dodecahedral outer core define the vertices of a cube (light green in Figure 2-3), the faces of which contain the remaining 12 Ag atoms in pairs (dark green in Figure 2-3) and are capped in such a way as to create an overall octahedral shape for the particle (Figure 2-3f). Namely, four sulfur atoms from the p-mba ligands are located on each face of the cube, such that the 24 sulfurs define a slightly distorted rhombicuboctahedron, an Archimedean solid (see Figure 2-3e). Each face then receives an additional Ag 2 S group to complete the inorganic part of the structure and the octahedral shape. The capping units are complex three-dimensional structures and unlike anything seen in gold clusters (1D) 8-12 or in silver-thiolate materials (2D). 26 They can be viewed most simply as an Ag 2 S 5 mount, with four S atoms acting as legs that connect it to the Ag 32 core. These four S atoms are bridged by a pair of Ag atoms, which are in turn bridged by a terminal S atom. Each sawhorse-shaped mount straddles a pair of Ag atoms (dark green in Figure 2-3) of the intact Ag 32 core. Altogether, six such Ag 2 S 5 mounts comprise the entire layer protecting the compact, quasi-spherical Ag 32 core. 21

39 22

40 Figure 2-3. X-ray crystal structure obtained from a Na 4 Ag 44 (p-mba) 30 crystal. (a) Complete cluster structure showing silver core and p-mba ligands (see colour scheme below). (b) Space-filling view down a 3-fold axis. Note face-to-face and edge-to-face pi stacking in the groupings of two and three ligands, resulting in considerable void space. (c, d) The Ag 32 excavated-dodecahedral core consists of an inner 12-atom (hollow) icosahedron (red) whose atoms do not contact sulfur, encapsulated by a 20-atom dodecahedron (green). The 8 atoms of the dodecahedron colored in light green define a cube, with pairs of dark green Ag atoms located above the faces. (e) Sulfur atoms are arranged in a slightly distorted rhombicuboctahedron with S atoms in the triangular faces coordinating to the light green Ag atoms of the 20-atom dodecahedron. (f) Six faces of the rhombicuboctahedron are capped with an Ag 2 S unit with the bridging S atom tilted off axis, completing the inorganic structure. (g) Two Ag atoms (dark green) on each face could be excised from the cluster to create Ag 4 S 5 capping mount structures, leaving a cubic Ag core. The distance between the two Ag atoms at the bottom of the mount and the nearest Ag atoms of the Ag 20 core is 2.83 Å, resulting in strong mount-to-core coupling. (h) An Alternative Ag 2 S 5 capping structure can be visualized as a sawhorseshaped mount that straddles the dark green Ag atoms of the intact dodecahedral Ag 32 core. The Ag 2 S 5 mount is better defined than the Ag 4 S 5 mount (see g) since its Ag atoms are separated by a larger distance (> 3.1 Å) from the nearest atoms of the Ag 32 core, resulting in a weaker mount-to-core interaction. Colour scheme: grey carbon; orange oxygen; blue exterior silver atoms in the mounts; gold bridging sulfur atoms in the mounts. For interatomic distances see the Appendix A. The two relatively exposed Ag atoms 27 on each side of the six mounts can acquire effective protection from the coordinating solvent, consistent with experimental observations. If this protection is lost, the clusters can polymerize to form larger plasmonic Ag nanoparticles. The uniqueness of this structure and the structural perfection of this cluster are reflected in its remarkable stability and its immunity to compositional changes. Further insight into the bonding and electronic structure of the Ag 44 (p-mba) 30 cluster was gained through extensive first-principles calculations. 27 Figure 4 shows the projected densities of states (PDOS, see Appendix A for details) calculated via density functional theory (DFT) based on the experimental configuration of the entire cluster (Figure 2-3a); the PDOS reflects the angular momenta (l) symmetries of the cluster s 23

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