Total Structure and Electronic Structure Analysis of Doped Thiolated

Sep 9, 2015 - In comparison, the reported total structures of thiolated Ag nanoclusters (e.g., [Ag44(SR)30]4–) contain surface structural motifs tha...
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Total Structure and Electronic Structure Analysis of Doped Thiolated Silver [MAg24(SR)18]2- (M = Pd, Pt) Clusters Juanzhu Yan, Haifeng Su, Huayan Yang, Sami Malola, Shuichao Lin, Hannu Häkkinen, and Nanfeng Zheng J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.5b07186 • Publication Date (Web): 09 Sep 2015 Downloaded from http://pubs.acs.org on September 9, 2015

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T Total Sttructure e and Ellectroniic Struc cture An nalysis of Dope ed 2T Thiolate ed Silve er [MAg24 ers 2 (SR)18 8] (M = Pd, Pt)) Cluste JJuanzhu Yan,1 Haifeng H Su,1 Huayan H Yang, 1 Sami Malola,2 Shuichao Linn,1,* Hannu Hääkkinen,2 Nanffeng Zheng 1,* 1

State Key Laborratory for Physicaal Chemistry of Solid S Surfaces, Collaborative C Innoovation Center oof Chemistry for Energy Materialls, and Enginneering Research Center for Nanoo-Preparation Technology of Fujiaan Province, Colllege of Chemistryy and Chemical EEngineering, Xiam men Universsity, Xiamen 3610005, China 2 Departments of Physics and Chemistry, Nanoscieence Center, Univversity of Jyväskyl ylä, FI-40014 Jyvääskylä, Finland SSupporting Inform mation A ABSTRACT: Withh the incorporatioon of Pd or Pt atom ms, thiolated Ag-riich 225-metal-atom nanoclusters were successfully s prepared and structuraally ccharacterized for thhe first time. Withh a composition off [PdAg24(SR)18]2- or [[PtAg24(SR)18]2-, thhe obtained 25-m metal-atom nanocllusters have a meetal fr framework structuure similar to that of widely investiggated Au25(SR)18. In bboth clusters, a M@Ag M ped by six distortted 12 (M = Pd,, Pt) core is capp ddimeric –RS-Ag-SSR-Ag-SR- units. However H the silveer-thiolate overlayyer ggives rise to a geom metric chirality att variance to Au25(SR)18. The effect of ddoping on the elecctronic structure was w studied througgh measured opticcal aabsorption spectraa and ab initio annalysis. This workk demonstrates thhat m modulating electroonic structures byy transition metall doping is expectted tto provide effectivve means to mannipulate electronicc, optical, chemiccal, aand catalytic propeerties of thiolated noble metal nanoclusters.

As miniatures of organic-cappedd metal nanopartiicles, atomically prreccise thiolated metaal nanoclusters haave attracted increeasing attention ovver tthe past several yeaars.1-4 Significant progress p has been made in the synthhessis and structural characterization of o thiolated Au annd Ag nanoclusteers. T The total structurees of an increasingg number of thiolaated metal nanocluus5 tters have been suuccessfully characcterized by X-rayy crystallography,5-18 m making it possiblee to deeply understand the structuree-properties correelattion at the molecuular level. Among the t large number of o total structures of tthiolated Au nanooclusters, the presence of surface ”staple” Au-thiolaate uunits (e.g., -RS-Au--SR-, -RS-Au-SR-A Au-SR-) has been commonly revealled. IIn comparison, thee reported total sttructures of thiolated Ag nanoclusteers ((e.g., [Ag44(SR)30]4-) contain surfacce structural motifs that are far moore ccomplicated than staple units onlyy.19-23 Such a strucctural feature makkes bboth the moleculaar and electronic sttructures of thiolaated Ag nanoclusteers qquite different from m those of thiolatted Au nanoclusteers. During the paast sseveral years, mucch effort has been devoted to the syynthesis and charaac2 tterization of Ag25(SR)18,24,25 and allso Ag-doped Au25(SR)18 clusters.26,27 FFor instance, conttinuous modulatioon of the electronnic structure of Auu25Agn(SR)18 has beeen achieved by continuously incorpporating up to 11 Ag A nA 27 aatoms into the nanoclusters. n Auu-rich Au25-nAgn(SSR)18 clusters weere ssynthesized and found to have a structure similaar to that of puure A Au25(SR)18.26 Many theoretical calcuulations also assum med that Ag25(SR R)18 w would take the sim milar structure as well. w 28,29 However, the t total structuree of tthiolated Ag-rich 25-metal-atom 2 nannoclusters has nott been experimenttallyy determined. h metal dopinng has been demoonstrated as an effeecOn the other hand, ttive strategy to modulate m the eleectronic structurees of thiolated Au A

nanocluusters, and thus theeir optical and posssibly catalytic prooperties.27,30-34 Consideerable efforts havee been made on ddoping Au25(SR)18 with Pd, Pt, Ag, Cu, Cd and Hg.27,30-33,,35 Each Au25(SR)18 cluster consists of a centered icosaheddral Au13 core cappped by six Au2(SR R)3 motifs.6,7 Enhaanced catalytic propeerties of the 25-atoom clusters has beeen demonstratedd by replacing the centtral Au atom in Auu25(SR)18 with Pdd or Pt.30,31 With thhe incorporation of PPd or Pt atoms, w we now demonstraate our success in the synthesis of two ddoped 25-metal-aatom nanoclusterss, [MAg24(SR)18]22- (M=Pd, Pt; SR=2,4--SPhCl2), and theeir total and electrronic structures. B Both clusters have a M M@Ag12 (M = Pd, Pt) core capped bby six heavily distoorted staple – RS-Ag-SSR- units. For thee first time, such distorted staple m motifs are revealed oon thiolated metaal nanoclusters. U Unexpectedly, thee presence of surface distorted staple motifs gives risse to a surface chirality on [MAg24((SR)18]2- (M = PPd, Pt). The U UV-vis absorptionn features of [PdAg244(SR)18]2- are systeematically red-shiifted as comparedd to those of [PtAg24((SR)18]2-.

Figure 11. The UV-vis (a) and ESI-MS (b) sspectra of the as-prrepared crude product of Pd-doped thioolated Ag nanocluusters. Inset in (b)) shows both experimeental and simulatedd high-resolution M MS spectra of the m major MS peak.

To incorporate Pd innto thiolated Ag naanoclusters, a moddified synthesis proceess of [Ag44(SR)300]4- was adopted.199 PdCl2 was introdduced together with A AgNO3 as the meetal precursors in the synthesis (see Supporting Informaation for details). IIn a typical syntheesis of Pd-doped A Ag nanoclusters, AgN gNO3 were dissolvved in methanol. Dichloromethanne and PdCl2 were thhen added to the solution to form m a mixture. The mixture was cooled to 0 °C in an ice bath, 2,4-dicchlorobenzenethiool and tetraphenylpphosphonium broomide (PPh4Br) w were then added. A After 20 min, NaBH4 aqueous solutionn and triethylaminne were added qquickly to the above m mixture under vigoorous stirring. Thhe reaction was agged for 12h at 0 °C. T The aqueous phasse was then remooved. The mixturre in organic phase w was washed severaal times with water for various charracterizations.

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[PdAg244(SR)18]2-, the Pdd–Ag distances beetween Pd and thhe Ag12 cage were avveraged at 2.748 Å Å, and the Ag–Agg bond lengths inn Ag12 cage in [PdAg244(2,4-SPhCl2)18]2- nanoclusters rangge 2.970 from 2.810 Å. With the incoorporation of Pd aat the center, the m metal-metal bondss in the icosahedral ccore have an averraged distance off 2.849 Å, slightly shorter than those (aaveraged at 2.87) in Au25(SR)18.6,7 On the surface oof Au25(SR)18, each of tthe six Au atoms iis linearly bound bby two SR with  S-Au-S ranging from m 171.8 to 174.1. In comparison w with the fairly lineear coordination of ssurface Au atom oon Au25(SR)18, the S-Ag-S bond angles of the 12 surfaace Ag atoms on [PdAg24(SR)18]2-- range from 1444.8 to 173.7, having a much bigger variiation. As a result, the six dimeric -R RS-Ag-SR-AgSR- surfface staple motifs are not planar anyy more (Figure 3A A and S5). In each staaple unit, at least onne of two terminaal SR- groups is heaavily deviated from thee plane defined byy the middle three atoms, -Ag-SR-Agg-.

A As clearly illustrateed in Figure 1a, thhe obtained crude product exhibitedd a U UV-vis absorptionn spectrum with tw wo well-defined molecule-like m opticcal ttransitions centereed with the two distinct peaks at 4883 nm and 628 nm. T The absorption spectrum s was diffferent from thosse of [Ag44(SR)30]4-, inndicating the form mation of new thioolated Ag nanoclussters. To chemicallyy identify its compposition, the obtainned nanocluster was w ccharacterized by electrospray ionizaation time of flightt mass spectromettry ((ESI–TOF–MS). As shown in Fiigure 1b, the as-pprepared Pd-doped tthiolated Ag nanoclusters displayedd three main peakss centered at m/z of 22950.21, 1606.12, 1320.25. The caareful analysis on the high-resolutioon m mass data revealedd that the strongest peak at m/z =22950.21 belonged to [[PdAg24(2,4-SPhC Cl2)18]2- whose isootopic pattern perrfectly matched the t ssimulation. The other o two majorr peaks were asssigned to [Ag5(2,4SSPhCl2)6]- and [Agg4(2,4-SPhCl2)5]-, respectively (Figuure S1), which couuld bbe fragments of thhe cluster or polym meric –Ag-SR- struuctures formed duurinng the synthesis. Both UV-Vis annd ESI-MS data clearly c indicated the t ppresence of high-ppurity [PdAg24(SR R)18]2- in the crude products. p

FFigure 2. The struucture of the [PdA Ag24(SR)18]2- clusteer revealed by X-rray ssingle crystal analyssis. (a) The overall structure s of the cluster. (b) The cappiing sstructure of six-disttorted dimeric -RS--Ag-SR-Ag-SR- surrface staple motifs on thhe centered icosahhedral Pd@Ag12 corre. Color legend: grreen and blue spherres, A Ag; orange sphere,, Pd; yellow spheree, S; grey sphere, C. All hydrogen and cchlorine atoms are omitted o for clarity.

Figure 33. The structures shhowing the importtant surface structuure features of [PdAg24 (SR)18]2-. (a) The structure highlighhting the interactioons within the six-distoorted dimeric surfaace staple motifs ((colored in red stiicks). Dashed sticks aree used to illustrate the Ag…S interactions between neighhboring motifs. (b) Thee structure showinng six  stacked ligand pairs on thee surface. The stacked ligand pairs are hiighlighted as red hhexagons connectedd by dash red lines.

It shhould be noted thhat the presence off distorted dimericc -RS-Ag-SRAg-SR- sstaple motifs on thhe surface of [PdA Ag24(SR)18]2- largeely altered the interactiions between neeighboring staple units. The two terminal SRgroups iin each dimeric staaple motif interactted with two Ag attoms from its two diffe ferent adjacent staaple motifs. Totallyy, there were thereefore 12 pairs of Ag…S interactions on tthe cluster’s surfacce. The Ag…S disttances ranged 2.777 frrom 3.330 Å withh an average of 3..006 Å (Figure 3aa and S6). In comparirison, the similar A Au…S contacts in A Au25(SR)18 were alll longer than 66,7 3.72 Å. With 12 pairs of Ag…S interacttions, [PdAg24(SR R)18]2- can be alternatiively structurally ddescribed as an iccosahedral Pd@A Ag12 core protected bby four triangular surface [(AgSR)3(SR)3/2] units. W We considered incorpooration of Pd iis the key to the successful synthesis of [PdAg244(SR)18]2- having a similar metal fram mework structure but distorted surface sstructure to that oof Au25(SR)18. Thee synthesis in the aabsence of Pd precursoor led to the forrmation of [Ag44((SR)30]2- as the m main product (Figure S7).

The high purity of [PdAg24(SR R)18]2- in the crudde products encouuraaged us to crystaallize them into single s crystals. Hiigh-quality dark-rred ssingle crystals (Figgure S2) containinng [PdAg24(SR)18]2- were obtained by sslowly diffusing heexane into the CH H2Cl2 solution of the doped nanocluustters at 0C. X-ray single s crystal analyysis did confirm thhe chemical formuula oof the [PdAg24(SR R)18]2- nanocluster and its -2 chargee. In the single cryys2ttals, [PdAg24(SR)18 ed with the countter 1 ] nanoclusters are co-crystallize + ccations, PPh4 , in a molar ratio of 1:2, into space grouup of P21/c (Figuure SS3). The thermoggravimetric analysiis (TGA) of the crystal c sample of the t ccluster was also carrried out to verify its composition. A total weight loss of ~~58.5 wt% (Figuree S4) was in perfe fect agreement witth the organic com mpponent of (PPh4)2[PdAg24(2,4-SPhhCl2)18] (organic,, 59.0 wt %; mettal, 441.0 wt %). Structurally, thhe [PdAg24(SR)188]2- nanocluster caan be described ass a ccentered icosaheddral Pd@Ag12 corre stabilized by siix distorted dimeric sstaple -RS-Ag-SR-A Ag-SR- motifs (Figure 2), having ann overall framewoork sstructure similar too that of Au25(SR)18.6,7 Several studiees have attempted to pprepare thiolated Ag-containing 255-metal-atom nanooclusters by doping A Au25(SR)18 with Ag A atoms and succeeeded in replacingg up to 11 Au atom ms w with Ag. This work represents the first successful structure determinatioon oof thiolated M25 cllusters consisting of Ag atoms as thhe major framewoork m metal atoms.

Anoother important ssurface structural feature of [PdAgg24(SR)18]2- is the pressence of strong … interactions between six pairss of benzene rings in thiolate ligands(FFigure 3b). Togethher with the Ag…S interactions discusseed above, such …  interactions heelp to lock the arrrangement of surface ligands and ccreate surface chhirality. In the crystals of [PdAg244(SR)18]2-, two enaantiomers with thee four surface [(Ag AgSR)3(SR)3/2] units arrranged in two difffferent orientationns (Figure S8). U Unfortunately, the two enantiomers werre 1:1 ratio to givve no circular dichhroism (CD) signals.

Ag24(SR)18]2- has a similar metal frramework to that of Although [PdA A Au25(SR)18, they shhow small variatioon in their detailedd core structure, but b ssignificant variattion in their detailed surfacce structures. In 2

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Journal of the American Chemical Society S12: thee upper edge of tthe Ag(4d)-band is at about -3.7 eV while the Pd(4d)//Pt(5d) dopant bband is located at aaround -2.5 eV.

An analogouss attempt was alsso made to synthhesize Pt-doped Ag A nnanoclusters. Wheen K2PtCl4 was used u to replace PdCl P 2 as the dopaant pprecursor, the obtaained nanoclusterrs showed a major mass peak centerred aat m/z of 2994.244 (Figure 4). Detailed analysis onn its high-resolutioon m mass data suggestted that the Pt-doped Ag nanoclustters had a compoosittion of [PtAg244(SR)18]2-. The presence of small s amount of [[Pt2Ag24(SR)18]2- was w also revealedd in the ESI-MS spectrum s of the asa pprepared Pt-doped nanoclusters. The T single crystal analysis confirm med tthat the obtained [PtAg24(SR)18]2- inndeed have a simiilar structure to thhat oof [PdAg24(SR)18]2-(Figure S9). Thee much heavier eleectron density at the t ccenter clearly sugggested that the cenntral atom should be b Pt. The second Pt aatom in [Pt2Ag23(SSR)18]2- should be located at any sitee of the 12 positioons aat the icosahedraal shell. Crystallographically, thee small amount of [[Pt2Ag23(SR)18]2- would w not be expeected to make deteectable contributioon tto the electron dennsities at the 12 attom positions of thhe icosahedral sheell. IIt should also be noted n that the peakk for [Pt2Ag23(SR))18]2- observed in the t EESI-MS spectra (FFigure S10) of disssolved crystals was much weaker thhan tthat of the crude product. p In some cases, c the peak wass even undetectabble. 2T These results sugggested that [Pt2Ag23 oor 2 (SR)18] should have relatively po sstability and thus would w not survivee much during thee crystallization prroccess.

Figuure 5 shows thatt both [PdAg24(SSR)18]2- and [PtxA Ag24-x(SR)18]2(x=1, 2)) exhibit broad m multiband optical absorptions in thhe UV−vis region. [PPdAg24(SR)18]2- dissplays two major absorption peakss centered at 483 andd 628 nm. In compparison, the two m major absorption peaks of [PtxAg24-x(SR R)18]2- (x=1, 2) weere blue-shifted too 453 and 564 nm,, respectively. Such a bblue shift in the opptical absorption is consistent withh the previous studies on Pd/Pt-doped Au25 nanoclusterrs. The calculatedd spectra are systemaatically red-shiftedd compared to thhe experiment, buut they reproduce vvery well the reelative shifts beetween [PdAg24(SSR)18]2- and [PtAg24((SR)18]2- in the tw wo lowest-energy ppeaks (Table S1). The lowestenergy peaks for [PdAgg24(SR)18]2- are syystematically red-shifted compared too the [PtAg24(SR))18]2-. This correlaates with the smalller calculated HOMO O-LUMO gap for [PdAg24(SR)18]2- (1.45 eV) vs. [PttAg24(SR)18]2(1.61 eV V).

Figure 5. Experimental (a) and compuuted (b) UV-Viss spectra of [PdAg24 (SR)18]2- and [PtA Ag24(SR)18]2- nanocclusters. In the theeoretical spectra, the inndividual optical trransitions have beeen folded into a sm mooth curve by using a G Gaussian width of 00.1 eV.

Thee calculations alsoo strongly indicated that Pd must bee at the center of [PdA Ag24(SR)18]2- althoough X-ray crystaallography cannoot distinguish well betw ween Pd and Ag. T The total energiess of three differentt structures of [PdAg244(SR)18]2- with thee Pd atom locatedd at the icosahedrral center, the icosaheddral shell, and thee surface metal-liggand shell were allso calculated for the ccomparison of theeir stabilities. Thee relative stabilitiees were calculated to be 0, +0.65, and +0.87 eV, respecctively, for the thrree structures with Pdd moving from thee center to the meetal-ligand shell. M Moreover, the calculateed optical spectraa on the structure with Pd doped att the icosahedral cennter matched the bbest with the meaasured data as com mpared to the other tw wo structures (Fiigure S13). Moreeover, a hypothettical all-silver [Ag25(SR R)18]- cluster withh the same structuure as [PdAg24(SR R)18]2- except replacinng the central Pd aatom by Ag was foound to have a callculated optical specctrum (Figure S114) very similar too that of [PdAg24(SR)18]2- and also prevviously reported sspectra of [Ag25(SSR)18]-.24,25 These rresults clearly suggesteed that all-silver [A Ag25(SR)18]- shoulld have a similar tootal structure as [PdA Ag24(SR)18]2- reporrted in this work.

FFigure 4. ESI-MS sppectra of the as-preepared crude produuct of Pt-doped thiolaated Ag nanoclusteers. The insets are the t corresponding high resolution speectra. Insets show botth experimental and simulated high-reesolution MS spectra oof the two major MS M peaks.

The doping off Pd and Pt alters the electronic struucture of the thiolateed Ag nanoclusterrs. As compared too Ag that containss one free valencee seelectron (d10s1 connfiguration), Pd has h a closed d-shelll but no s-electroons ((d10s0) while Pt haas both d and s sheells open (d9s1). It is then of interest to sstudy how these trransition metal doopants contributee to the overall eleec2ttronic structure off the [MAg24(SR)18 o the frontier orbbit1 ] . Our analysis of 2aals of [MAg24(SR))18] (M=Pd, Pt) clusters c show unam mbiguously that the t cclusters have overaall 8 free valence electrons, e namely,, the 3-fold degeneeraate HOMO state is i a superatom 1P,, and the lowest em mpty superatom 1D 1 sstates are split in 2-fold 2 LUMO andd 3-fold LUMO+1 manifolds just as in 7 tthe previous case of [Au25(SR)18]-.7,36 Thus the clustters obey the wideely aapplied superatom m rule (Figure S111).37 It is importannt to realize that the t 224-18+2=8 electroon count for [MA Ag24(SR)18]2- (M=P Pd, Pt) comes froom tthe 24 Ag(s) electtrons, minus 18 electrons e withdraw wn by the thiolattes, pplus two extra electrons from the overall o negative chharge, implying thhat bboth Pd and Pt actt as zero-valent doopants in these cluusters. Pt thus acts as a closed d-shell d100s0 element as doppant, not d9s1 as inn the free atom. The rrelative positions of o the Ag and Pd//Pt d-electrons arre revealed in Figuure

As observed directtly from the ccrystal structure analysis of [MAg24((SR)18]2-, the silveer-thiolate overlayyer imposes geometric chirality and botth enantiomers arre present 1:1 in thhe crystal unit celll. Figure S15 shows thhe calculated CD spectra for one ennantiomer of [PdA Ag24(SR)18]2- , [PtAg24((SR)18]2- and the hypothetical [Ag225(SR)18]- discussed above. All the clussters have also verry similar CD speectra, where the ssignals in the range off 450 – 900 nm aare red-shifted in [PdAg24(SR)18]2- compared to [PtAg24((SR)18]2-. Our callculation serves hhere as a predictioon for experimental CD spectra in ccase that the enaantiomeric separaation will be achievedd in the future expperiments.38 To summarize, by inntroducing Pd or PPt, thiolated Ag-riich 25-metalatom naanoclusters with a composition of [M MAg24(SR)18]2- (M=Pd or Pt) have beeen successfully syynthesized and sttructurally identiffied by X-ray 3

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diffraction. Both clusters can structurally described as a M@Ag12 (M = Pd, Pt) core capped by six distorted dimeric –RS-Ag-SR-Ag-SR- staple units, having a metal framework structure similar to that of the widely studied [Au25(SR)18]- cluster. Ag-rich thiolated 25-metal-atom nanoclusters has been long pursued but not structurally characterized. This work has clearly demonstrated the importance of metal doping in tuning electronic structures of metal nanoclusters. Modulating electronic structures by transition metal doping is expected to provide effective means to manipulate electronic, optical, chemical, and catalytic properties of thiolated noble metal nanoclusters.

ASSOCIATED CONTENT Supporting Information. Experimental details, detailed crystallographic structure and data including the CIF file, computational details, analysis of the cluster electronic structure, TGA, and more mass spectra. This information is available free of charge via the internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author

[email protected], [email protected]

ACKNOWLEDGMENT We thank the MOST of China (2011CB932403, 2015CB932303) and the NSFC of China (21420102001, 21131005, 21390390, 21227001, 21333008) for financial support. The work in University of Jyväskylä was supported by the Academy of Finland (266492). The computations were made at the CSC computing center in Espoo, Finland.

REFERENCES Jin, R. Nanoscale 2015, 7, 1549. Qian, H. F.; Zhu, M. Z.; Wu, Z. K.; Jin, R. C. Acc. Chem. Res. 2012, 45, 1470. Häkkinen, H. Nat. Chem. 2012, 4, 443. Tsukuda, T. Bull. Chem. Soc. Jpn. 2012, 85, 151. Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Bushnell, D. A.; Kornberg, R. D. Science 2007, 318, 430. (6) Heaven, M. W.; Dass, A.; White, P. S.; Holt, K. M.; Murray, R. W. J. Am. Chem. Soc. 2008, 130, 3754. (7) Zhu, M.; Aikens, C. M.; Hollander, F. J.; Schatz, G. C.; Jin, R. J. Am. Chem. Soc. 2008, 130, 5883. (8) Qian, H. F.; Eckenhoff, W. T.; Zhu, Y.; Pintauer, T.; Jin, R. C. J. Am. Chem. Soc. 2010, 132, 8280. (9) Das, A.; Li, T.; Nobusada, K.; Zeng, C.; Rosi, N. L.; Jin, R. J. Am. Chem. Soc. 2013, 135, 18264. (10) Dass, A.; Theivendran, S.; Nimmala, P. R.; Kumara, C.; Jupally, V. R.; Fortunelli, A.; Sementa, L.; Barcaro, G.; Zuo, X.; Noll, B. C. J. Am. Chem. Soc. 2015, 137, 4610.

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