SUPPORTING INFORMATION

Transcription

1 SUPPORTING INFORMATION Table of Contents S1 1. General materials and methods S2 2. Syntheses of {Pd 84 } and {Pd 17 } S3-S4 3. MS studies of {Pd 84 }, {Pd 17 } and the two-component reactions S5-S6 4. Characterization of {Pd 84 }: IR, NMR, UV and TGA S7-S8 5. The hypothetical polyoxopalladate cluster, {Pd 60 } S9 6. Still + Legend for the assembly movie Pd Conversions (full).avi S9 7. References S9

2 1. General Materials and Methods All chemicals and solvents were used as purchased without further purification. Flame Atomic Absorption Spectroscopy Analysis: FAAS analysis was performed at the Environmental Chemistry Section, School of Chemistry, The University of Glasgow on a Perkin-Elmer 1100B Atomic Absorption Spectrophotometer. 1 H/ 31 P/ 13 C-Nuclear magnetic resonance spectroscopy ( 1 H/ 31 P/ 13 C-NMR): 1 H/ 31 P/ 13 C-NMR spectroscopy was performed on a Bruker DPX 400 spectrometer using the solvent signal as internal standard. All δ values are given in ppm. Infrared Spectroscopy: All IR experiments were carried out with a Shimadzu FTIR 8400S. Mass spectrometry: Measurements were made using a) Bruker micro ToFQ in negative ion mode; b) Waters Synapt G2 HDMS in sensitivity-mode equipped with a Quadrupole and Time-of-flight (Q/ToF) module for MSanalysis. Microanalysis: Carbon, nitrogen and hydrogen content were determined by the microanalysis services within the School of Chemistry, University of Glasgow using a EA 1110 CHNS, CE-440 Elemental Analyzer. Single Crystal X-Ray Diffraction: Single crystal datasets and unit cells were collected at 150(2) K on a Bruker Apex II Quasar diffractometer equipped with a graphite monochromator (λ (Mo Kα ) = 0.71 Å). Structure solution and refinement was carried out using SHELXL-97 1 and WinGX 2 via a full matrix least-squares on F 2 method 3. All non-hydrogen atoms were refined anisotropically unless otherwise stated. This data can be obtained free of charge from CSD for compound {Pd 84 } from CCDC, Cambridge, UK; deposit@ccdc.cam.ac.uk, CCDC Thermogravimetric Analysis: TGA was performed on a TA Q500 instrument under a nitrogen atmosphere. UV-Vis spectroscopy: UV-Vis spectra were collected using a JASCO V-670 spectrometer equipped with an ISV723 60mm integrating sphere in diffuse reflectance mode.

3 2. Syntheses of {Pd 84 } and {Pd 17 } Synthesis of {Pd 84 }: NaH 2 PO 4 -Na 2 HPO 4 solution (22 ml, 0.15 M) at a ph of was added to Pd(OAc) 2 (0.56 g, 2.5mmol). The suspension was left stirring rigorously for 20 hours. The dark red solution was centrifuged and filtered to remove a small amount of solids. The ph of filtration then needed to be checked, and a few drops of 1M NaOH were added to adjust the ph to 4.5. Evaporation of the filtrate from an open beaker led to well-formed reddish long needle crystals after a few days. The crystals were collected by filtration and airdried. Yield: ca % (based on Pd); 31 P-NMR (400MHz, D 2 O) δ 22.0, 15.7 ppm; 13 C-NMR (400MHz, D 2 O) δ 187.7, 186.1, ppm; IR: 3300, 2300, 2060, 1550, 1510, 1400, 1350, 950, 875, 690 cm -1 ; Elemental analysis, Calc. for C 56 H 498 Na 56 O 466 P 42 Pd 84, C 3.3%, H 2.5, Na 6.4%, P 6.5%, Pd 44.4%; Found C 3.7%, H 1.3%, Na 6.5%, P 6.7%, Pd 44.3%. Synthesis of Na 9 [Pd 2 {H 7 Pd II 15O 10 (PO 4 ) 10 }] ({Pd 17 }) 4 : NaH 2 PO 4 -Na 2 HPO 4 solution at a ph of 6.5 (22 ml, prepared from adding 1M NaOH to 0.15 M solution of NaH 2 PO 4 ) was added to Pd(OAc) 2 (0.56 g, 2.5mmol). The suspension was left stirring rigorously and heating to 85 ºC for 90 min. After the heating, the dark black solution was cooled to room temperature (ph=4.0) and filtered to remove a small amount of black solids. Slow evaporation at room temperature led to some black needle crystals after 2 weeks. The crystals were collected by filtration and air-dried. Yield: ca. 5% (based on Pd). Figure S1: Wire model of the subunit, {Pd 6 }, of the cluster anion {Pd 84 }, which consists of a {Pd 6 (μ 4 -O) 2 } core (blue tetrahedra), two capping PO 4 3-, a μ 2 -O, two CH 3 COO - and a bridging PO Figure S2: Comparison of the Pd-Pd distances in the virtual building blocks of {Pd 6 }. Left: the geometry of the {Pd 6 } metal core. Right: typical distances in each subunit, showing two different types of Pd-Pd: Å (1-5, 7-11) and 2.9 Å (6).

4 3. MS Studies of {Pd 84 }, {Pd 17 } and the two-component reactions Figure S3: MS spectra of a) Pd(OAc) 2 +NaH 2 PO 4 /Na 2 HPO 4 solution without heating (25 C); b) Pd(OAc) 2 +NaH 2 PO 4 /Na 2 HPO 4 solution with heating (85 C); c) single crystals of {Pd 84 } in water; and d) single crystals of {Pd 17 } in water.

5 Figure S4: MS spectrum of the mixture of Pd(OAc) 2 +NaH 2 PO 4 /Na 2 HPO 4 solution without heating (25 C), revealing a significant envelope of very high nuclearity highly charged molecules in the mass range of kd.

6 4. Characterization of {Pd 84 }: IR, 13 C/ 1 H/ 31 P-NMR, UV and TGA %Transmittance Wavenumbers (cm -1 ) 600 Figure S5: IR spectrum of {Pd 84 }, showing two sharp characteristic peaks of carboxylate at the wavenumber 1550 and 1440 cm -1.

7 Figure S6: 13 C-NMR of a) sodium acetate and b) {Pd 84 } in D 2 O ppm ppm Figure S7: 1 H-NMR and 31 P-NMR of {Pd 84 } in D 2 O

8 Absorption Wavelength Figure S8: UV-Vis spectrum of {Pd 84 } in aqueous solution (0.005 mm). Sample: fx7702 Size: mg Method: Ramp Comment: 10C/min to 800 in N2 100 TGA File: U:\group\Feng Xu\Data\TGA\fx Operator: Feng Xu Run Date: :31 Instrument: TGA Q500 V6.7 Build % Weight (%) % Deriv. Weight (%/ C) Temperature ( C) Figure S9: TGA plot of {Pd 84 } Universal V4.1D TA Instruments

9 5. The hypothetical polyoxopalladate cluster, {Pd 60 } Figure S10: The negative ion mass spectrum of the as-prepared {Pd 84 } mother liquid, showing the extreme complexity of the solution with a great number of different highly-charged species. By careful examination of the spectrum, the peak at m/z = can be found and assigned to a 8 - -charged species with the typical formula [(Pd 5 O 5 ) 12 (PO 4 ) 30 H 35 Na 47 (H 2 O) 45 ] Legend for the movie Figure S11: Still from the movie Pd Conversions (full).avi which shows the hypothetical assembly of the {Pd84} wheel from the {Pd17} and highlights the transferable building blocks. Assembly of the predicted {Pd60} is also shown with reference to the building blocks in the {Pd17}. 7. References (1) Sheldrick G, (2008) A short history of SHELX. Acta Crystallogr., Sect. A: Found. Crystallogr 64: (2) Farrugia F, (1999) WinGX Suite for Single Crystal Small Molecule Crystallograph, J. Appl. Crystallogr 32: (3) Clark RC, Reid JS, (1995) The analytical calculation of absorption in multifaceted crystals, Acta Crystallogr., Sect. A: Found. Crystallogr 51: (4) Cronin L et al. (2011) A Supramolecular Heteropolyoxopalladate {Pd 15 } Cluster Host Encapsulating a {Pd 2 } Dinuclear Guest: [Pd II 2 {H 7 Pd II 15O 10 (PO 4 ) 10 }] 9-. J Am Chem Soc 133(13):