Supporting Information A Highly Efficient Luminescent Metal-Organic Framework for the Simultaneous Detection and Removal of Heavy Metals from Water ‘Nathan D. Rudd,* Hao Wang,* Erika M.A. Fuentes-Fernandez,* Simon J. Teat,’ Feng Chen,§ Gene Hall,t Yves J. Chabal* and Jing Li** * Departmentof Chemisty and Chemical Biology, Rutgers University, 610 Taylor Rd, Piscataway, NJ 08854, USA # Department of Materials Science and Engineering, University of Texas at Dllas, 800 W Campbell Rd, Richardson, TX 75080, USA “Advanced Light Source, Lawrence Berkeley National Laboratory, I Cyclotron Rd, Berkeley, CA 94720, USA Department of Chemistry, Biochemistry and Physics, Rider University, 2083 Lawrenceville Ré, Lawrenceville, NJ O8648, USA. *Comespondng Autor: jigliugersedsTable of Contents SL. Materials Usediunnnnennnnnnannnen snesnnnnenninmnnennininnnnnnrnnmnennnmnnrnied 2. Powder X-ray Diffraction (PXRD) Analysis of LMOF-261, -262 and -263. 6 $3. Thermogravimetric Analysis of LMOP-261, -262 and -263 .n S4, Optical Characterization of LMOF-261, -262 and -263., 85, Pore Characterization of LMOF-261 and -263... $6, Inductively Coupled Plasma Optical Emission Spectroscopy. S7. X-ray Fluorescence Spectroscopy anno $8. Fourier Transform Infrared Spectroscopy .snu:nnnnannnnnamnnnsnsnunann $9, X-ray Photoelectron Spectroscopy. S10, Stetn-Volmer Curves for Hg” and Pb** S11, Limit of Detection for Hg? and Pb... stn 22 S12, References sennList of Figures Figure S1. Crystal images of a) LMOF-261 and b) LMOF-262.0 nnn Figure $2. LMOF-263 is stable under a variety of conditions, including a) in water for 24 h and b) 2 weeks. Also, LMOF-263 stayed relatively stable exposed to pH c) 4, d) 6, ¢) 8 and f) 10 for 15 h, with the low angle peaks showing increased crystallinity under basic conditions... Figure $3. Thermogravimetric ('G) analysis of as-made LMOF-261 (green), -262 (purple) and -263 (red)..7 Figure $4, Optical absorption spectra (converted to KM Function) of as-made LMOF-261 (green), -262 (purple), -263 (red) and 4-tppe (blue) 8 Figure $5. Optical emission and excitation spectra for outgassed LMOF-261 (green), -262 (purple) and -263 (red), Values in parentheses provide the emission or excitation wavelength at which the displayed excitation or emission spectra, respectively, were monitored. ‘The emission maxima of outgassed samples of LMOP- 261, -262 and -263 are at 538, 528 and 516 nm, respectively. oe] Figure $6. (a) PL intensity ratios of LMOF-263 at each Hg adsorption and desorption stage of the recy- cling cycle, and (b) the PXRD pattems after each full cycle to show LMOF-263 stability after the recycling proces 10 Figute $7. No adsorption and desorption isotherms for a) LMOF-261 and b) LMOF-263. ¢) The H-K mi- cropore size distribution analysis of LMOP-261, indicating micropores in the range of 5-10 A, al Figure $8. CO. adsorption and desorption isotherms for LMOP-261 and -263. Uptake maxima increased from LMOF-261 to -263, with 1.60 and 2.22 mmol/g, respectively smn 12 Figure $9. (@) Hy concentrations after exposure to LMOF-263 for various time intervals. (b) ‘The amount of adsorbed Hg as a function of exposure time, The inset shows the pseudo-second-order kinetic plot for Hg adsorption (intial Hg?* concentration: 10 ppm). 13 Figure S10, PXRD overlay of LMOF-26 amples, demonstrating structural effects with increased exposure to Hg 14 Figure $11. FTIR spectra of LMOF-261 and -263. Black labels are used to identify peaks related to the sulfone moiety (LMOF-263), while blue labels show peaks concerning the carbonyl group (LMOF-261).. 15 Figure $12. XPS spectsa for as-made LMOF-263.... se NG Figure S13, XPS spectra of LMOF-263 exposed to water (no Hg). The binding energies for carbon, oxygen and sulfur don’t change from the as-made LMOF-263 data, indicating changes in the binding energies must, occur due to interactions with Hg’. No trace Hy” is detected in the water used throughout the analysis..16 $3Figure S14, XPS spectra of LMOF-263 exposed to 100 ppm Hi Figure S15. XPS spectra of LMOF-263 exposed to 1,000 ppm Hy" Figure $16, XPS spectra of LMOF-263 exposed to 10,000 ppm Hg" 18 Figure S17. XPS spectra of LMOF-263 exposed to 30,000 ppm He” 18 Figure $18. XPS spectra of LMOF-263 exposed to 20,000 ppm Mg” 19 Figure S19, Overlayed XPS spectra of LMOF-263 exposed to incremental Hg” concentrations. The sulfur binding energy increases (curves shift to the right) when exposed to higher Hg" concentrations. wn 20 Figure $20, Stern-Volmer curves for LMOF-261, -262 and -263 after exposure to Hg" through fluores cence titrations... se Figure $21. Stern-Volmer curves for LMOP-263 when exposed to a) Hg” and b) Pb", Error bars indicate the average standard deviation of li/I values between multiple trials of each metal ion Figure $22. Emi ion spectra from the low concentration fluorescence titration of LMOF-263 with aliquots 23 of Hg” solution, with enhanced detail provided in the inset... S4List of Tables ‘Table S1. IQY data for as-made and outgassed samples of LMOF-261, -262 and -263 under 360 nm excita- tion. 9 “Table $2. XRF data from a 50:50 (w/w) mixture of HgCl:ZnO and as-made LMOF-26: 13 ‘Table 53. Relative molar ratios of Hg”*:Zn”* in LMOF-263 after exposure to vatious Hg"* concentrations. Values represent averages over three trials 14 ‘Table $4, Summary of XPS data for LMOF-263 exposed to various Hg” and Mg” concentrations. 19 ‘Table 5. The percent atomic concentration at each oxygen core level over multiple Hy”* and Mg’* expo sure CONdIIONS snmninmnineninnsnnn ue 20 SsS1. Materials Used Ultrapure, deionized water was obtained through a Direct-Q Water Purification System (EMD Millipore) at a 0.5 L/min flow rate, and was used for all detection and uptake experiments. Reagents and solvents were used as received from: Alfa-Aesar—{1,1,2,2-tetraphenylethylene (98%), bromine liquid (99.8%), tricyclohex. yiphosphine (98%), magnesium sulfate (09%), dichloromethane (99.5%), methanol (99.9%), palladium(1T) ac~ erate (99.98%), dimethyl sulfoxide (99%), 2-propanol (99.5%), hydrazine monohydrate (98%), sodium hy- droxide (98%), ethylene glycol (98%), chlorosulfonic acid (99%)]; Oakwood Chemical—{dimethylformamide (99.5%), dimethylacetamide (99%), chloroform (99.8%)]; Sigma-Aldrich—[zine({I) nitrate hexahydrate (99% potassium phosphate tribasic (98%), pyridine-4-boronic acid (90%), biphenyl-4,4"-dicarboxylate dimethyl es- ter (07%)]; TransWorld Chemicals—[9-fluorenone-2,7-dicarboxylic acid (96%) Metal salts for detection and adsorption studies were used as received ftom: Alfa-Aesar—[lead(Il) chloride calcium chloride (97%), mercury(II) chloride (98%)]; Fisher Scientific—{magnesium chloride (99%)] $2. Powder X-ray Diffraction (PXRD) Analysis of LMOF-261, -262 and -263 Powder X-ray diffraction (PXRD) analyses were performed using a Rigaku Ultima-IV- diffractometer at room temperature under Cu K, radiation (A = 1.5406 A). Data were collected from 3-45° 26, with the operating power set to 40 Kv/44 Ma. The scan rate was 2° 20/min, with a step size of 022° 26 PXRD patterns (Figure 2) were obtained for the as-made crystal samples shown in Figure S1. The crystal morphologies change slightly within the isoreticular series, yet the PXRD patterns contained identical peaks (Figure 2). Crystal colors were consistent with the color of the dicarboxylate linker used in the solvothermal reaction. Only powder samples of LMOF-263 could be synthesized for this analysis. Figure S1. Crystal images of (a) LMOF-261 and (b) LMOF-262. Figure S2 portrays the remarkable stability of LMOF-263 at various pH values and water exposure times. The material was stable in water for 2 weeks, and rel S6—Simulatd patter LMOF-263 ae-made Intensity (counts) 20°) Figure $2, LMOF-263 is stable under a variety of conditions, including a) in water for 24 h and b) 2 weeks. Also, LMOF-263 stayed relatively stable exposed to pH c) 4, €) 6, &) 8 and f) 10 for 15 h, with the low angle peaks showing increased crystallinity under basic conditions. $3. Thermogravimetric Analysis of LMOF-261, -262 and -263 ‘Thermogravimetric analysis (TGA) was performed using a TA Instruments Q5000 under constant No flow (20 mL/min). Approximately 4 mg of sample was placed into a platinum pan, which was then heated from 30-600 °C ata rate of 10 °C/min. Figure $3 displays the three TGA curves for each member of the isoretie- ular series. x z 3 z ‘Temperature °C) Figure $3. Thermogravimetric (TG) analysis of as-made LMOF-261 (green), -262 (purple) and -263 (red). S7$4. Optical Characterization of LMOF-261, -262 and -263 UV-visible diffuse reflectance spectra were obtained for LMOF-261, -262, -263 and the fluorescent ligand 4- tppe at oom temperature using a Shimadzu UV-3600 spectrophotometer. ‘The diffuse reflectance data was converted to the Kubelka-Munk Function as follows: a FR) = aR Equation $1, Kubelka-Munk function F(R), where R is the diffuse reflectance. 2 Plotted in Figure $4 are solid-state diffuse reflectance spectra for the three LMOFs and tppe. The estimated bandgap is redshifted as tppe is incorporated into the LMOFs. os 04 03 KM Function os 22 2 a2 Energy (eV) Figure $4, Optical absorption spectra (converted to KM Function) of as-made LMOF-261 (green), -262 (purple), -263 (red) and 4-tppe (blue). Using a Varian Cary Eclipse spectrophotometer, optical excitation and emission spectra were collected for outgassed solid samples of LMOP-261, -262 and -263, depicted in Figure $5. The emission for each LMOF was red-shifted upon outgassing, Outgassed LMOF-263 demonstrates the most drastic red-shift from the as- made sample, changing from blue to green emission (Rem, acmade = 464 1m, Nem, ougassed = 516 nim) with 365 nm excitation, LMOF-261 red-shifted from green to yellow emission (lem, asmade = 514 nm, Rem, otgssed = 538 ‘am) while the emission from LMOP-262 red-shifted from 515 nm to 528 nm upon outgassing. SsMOF 261406 emiesion (88 nm) oa Wvelength (om) Figure $5. Optical emission and excitation spectra for outgassed LMOF-261 (green), -262 (purple) and -263 (red), Values in parentheses provide the emission or excitation wavelength at which the displayed excitation or emission spectra, respectively, were monitored. The emission maxima of outgassed samples of LMOF- 261, -262 and -263 are at 538, 528 and 516 nm, respectively. Internal quantum yield (IQY) was measured using a Hamamatsu C9220-03 spectrophotometer with integrat- ing sphere. Table $1 displays IQY data upon 360 nm excitation, ‘Table S1. IQY data for as-made and outgassed samples of LMOF-261, -262 and -263 under 360 am excita- tion, TOY (%) As-made Outgassed LMOF-261 18.2 95 LMOF-262 107 102 LMOF-263 89.2 76.6 Recyclability is an important characteristic of materials used in environmental remediation, as these adsor- bents can be reused if Hg” adsorption is reversible. Previously, solutions with high acidity have been used to extract Hg” from an adsorbent. In this case, a 1M CS; solution was used to extract Hg” from LMOF-263, Since CS: is not miscible with water, 2-propanol was used to first dissolve the CS:, then the resulting solution was added to the aqueous solution of Hg" @LMOF-263. Shown in Figure S6a, the PL intensity of LMOF- 263 after the first CS: exposure was 95% of the as-made LMOF-263 intensity (lo). After another full adsorp. tion-desorption cycle, the PL intensity was 92% of Is. The PL. data is consistent with the PXRD overlay of LMOP-263 after each cycle (Figure S6b)—the structure was stable after two full Hg” adsorption and desoxp. tion cycles. soa Lo ~ rot eres 3 o 2 2 ° 7 7 b 2 oyete ths) Figure S6. (2) PL intensity ratios of LMOF-263 at each Hg” adsorption and desorption stage of the re cling cycle, and (b) the PXRD patterns after each full cycle to show LMOF-263 stability after the recycling process. $5. Pore Characterization of LMOF-261 and -263 Gas sorption isotherms of outgassed LMOF-261 and -263 were collected on a Quantachrome Instruments Autosorb-1 MP volumetric gas sorption analyzer using ultra high purity No (99.999%). Liquid nitrogen was used as coolant to achieve cryogenic temperature (77 K). The No isotherm was collected in a pressure range from 10” to 1 atm, The BET surface area was obtained using Autosorb v1.50 software. LMOP-261 and -263 were ourgassed by heating the samples at 120 °C for 6 h. LMOP-262 was not stable upon outgassing, so the material was excluded from gas adsorption analyses. Nz adsorption isotherms for LMOF-261 and -263 are depicted in Figure $7. BET surface areas were determined to be 977 and 1004 m°/g for LMOF-261 and -263, respectively. S10I He no ston i. 2 Deron Somerton : oe 7 Te ees a es {- io cy ra = % ‘Pore With (A) Figure $7. Nz adsorption and desorption isotherms for a) LMOF-261 and b) LMOP-263. c) The H-K mi- cropore size distribution analysis of LMOF-261, indicating micropores in the range of 5-10 A. CO: adsorption and desorption isotherms (room temperature) were obtained for LMOF-261 and -263. Figure $8 shows the CO; adsorption isotherm overlay, Uptake maxima were recorded at 1.60 and 2.22 mmol/g for LMOF-261 and -263, respectively. The higher CO: uptake for LMOF-263 is consistent with its larger BET surface area. ‘The micropore volumes for LMOF-261 and -263 were 0.27 and 0.32 em’/g, respectively—also consistent with the BET surface area values. The micropores would be wide enough to incorporate partially or fully solvated Hg” ions, respectively. Su‘e LHoF-261 adsorption ‘OLMOF-261 Derorption ‘© LMOF-263 Adsorption 25) (LMOF-263 Desorption Uptake (mmoUg) ° os 7 Pressure (bar) Figure $8, CO: adsorption and desorption isotherms for LMOF-261 and -263. Uptake maxima increased from LMOF-261 to -263, with 1.60 and 2.22 mmol/g, respectively. $6. Inductively Coupled Plasma Optical Emission Spectroscopy Inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses were performed using a Spec- tro Arcos Analyzer with standards from VHG Labs (#SM45-500 and SM70B-500). ICP-OES was used to determine the concentrations of various metal ions (Hg’*, Pb’, Ca®* and Mg’) in aqueous solutions after various LMOF-263 exposure conditions. ‘The rate at which LMOF-263 removes Hg” from solution has been analyzed. Figure $9a shows the relatively fast kinetics observed when 15 mg of LMOF-263 was exposed to 10 ppm Hg” solutions for various time intervals, Approximately 99.1% of the initial amount of Hg" was removed after just 30 min, and 99.4% removed after 15 h. The minimal improvement after 30 min indicates the efficiency of Hy” adsorption. The experimental data were fitted with the pseudo-second-order kinetic model using the below equation.’ t 1 S t % Keg Equation $2. Pseudo-second-order kinetic model, where k: (g mg min") is the adsorption rate constant, q (mg g') is the amount of Hg”* adsorbed at time t (min), and q. (mg g') is the amount of Hg”* adsorbed at equilibrium, ‘The value of the adsorption rate constant ke was determined to be 0.295 g mg! min", and a high correlation coefficient (20.999) was obtained when the data was fit with the kinetic model (Figure $9b). S120 8 Hg) Concentration (pm) ‘Adsorbed Amount (mg 6) . “Time min) 2 Tie min) Figure $9. (a) Hg” concentrations after exposure to LMOF-263 for various time intervals, (b) The amount of adsorbed Hg” as a function of exposure time. The inset shows the pscudo-second-order kinetic plot for He" adsorption (initial Hg?* concentration: 10 ppm). $7. X-ray Fluorescence Spectroscopy X-ray fluorescence spectroscopy (XRF) measurements were performed on a Horiba X-ray Analytical Micro- scope XGT-1000WR, with X-ray tube voltage and current at 50 kV and 60 uA, respectively. XRF was utilized to detetmine the relative amounts of Zn?' and Hg" in LMOF-263 after various Hg" exposure conditions. As a control, a mixture of ZnO and HgCh (50:50 weight ratio of Zn:Hg) was prepared to make sure the instrument was calibrated properly. The molar ratio between Zn and Hg in the mixture was 1:0.280, which corresponds to a relative mass of 53.83 and 46.17%, respectively (Table $2). The difference between an exact 50:50 ratio can be attributed to ertor when weighing out the powders. For further control, relative masses of zine and sulfur in as-made LMOF-263 were determined (Table $2). ‘The LMOF-263 formula [Zn.(dbtdeO:):tppe|, derived from SCXRD analysis on the isoreticular LMOF-261, reveals an equimolar amount of zinc and sulfur. The relative weight percentages of zinc and sulfur in the as- made samples averaged to 67.22 and 32.78%, respectively, or a molar ratio of 1:0,995, consistent with the structural analysis. ‘Table $2. XRF data from a 50:50 (w/w) mixture of HgCl:ZnO and as-made LMOF-263. 50:50 Mixture of HgCl:ZnO ‘As-made LMOF-263 Element Molar Ratio Weight eae Element Molar Ratio. Weight nae Zn T 3383 Zn 7 6722 Hg 0.280 46.17 s 0.995 32.78 LMOF-263 (15 mg) was exposed to 35 mL-solutions of various concentrations of Hg” (10, 100, 1000, 10,000, 20,000 and 30,000 ppm) for 36 bh. XRF was used to determine the relative amounts of zine and mercury in the filtered and washed powder (Table $3). The data is plotted in Figure 7 with an average standard deviation of £0.152 molar ratio HgZn, S13‘Table $3. Relative molar ratios of Hg”: Values represent averages over three trial n°" in LMOF-263 after exposure to various Hg” concentrations, Hg™ Concentration (ppm) 10 100 1000 10,000 20,000 30,000 Element Molar Ratio Zn 7 7 7 7 T 7 Hg 0.25 oa? 0.76 0.88 1.19 1.30 ‘The maximum molar 1:1.3 ZnsHg) after exposure to 30,000 ppm. Since Zn** is equimolar with sulfur, the ratio 1:1.3 (S:Hg) is justified. The uptake capacity is estimated to be 380 mg Hy”*/g. ‘The structure of LMOP-263 remains stable after exposure to the Hg” concentrations listed in Table $3. Figure $10 exhibits the PXRD overlay of the filtered adsorbents after exposure to cach He” concentration. ‘The sharp peak observed around 4.5° 20 in the simulated pattern is enhanced after Hg” exposure, This same phenomenon was seen after exposure to basic conditions (Figure $2). The presence of adsorbed species in MOF channels has been shown to increase low-angle diffraction peaks," whether it be Hg” ions (from ad- sorption experiments) or by-products from the base-catalyzed hydrolysis of solvent guest molecules (base- exposure experiments). uated MOF 261 haem te —toerppm Ha 100 pom 808 pen a = 3e.000 pn 3 ° 2 2 2c) Figure S10. PXRD overlay of LMOF-263 samples, demonstrating structural effects with increased exposure to Hg. $8. Fourier Transform Infrared Spectroscopy Fourier transform infrared (FTIR) spectroscopy was used to identify the different functional groups in LMOF-261 and LMOF-263. For these measurements, the LMOF-263 powder was gently pressed onto a KBr peller (~1 cm diameter, 1-2 mm thick). The pellet was placed into a high-pressure, high-temperature cell (product number P/N 5850c, Specac Ltd., UK) at the focal point of an IR spectrometer (Nicolet 6700, ‘Thermo Scientific, US). ‘The samples were activated by annealing under vacuum (<50 mTorr) at 100 at least 1 h, then cooled down to room temperature for FTIR analyData were collected on pristine samples of LMOF-263 and LMOF-261 (the parent structure). Sulfur-related vibrational modes were clearly identified for the LMOF-263 sample, and carbonyl modes observed for LMOF-261. In Figure $11, all the vibrational modes in the two pristine samples are shown in the 6100-1800 cm’ spectral range with the most important modes assigned and libeled as described below. — LMoF-263 cee = tworzs1 S=0 str 1170.0m+ 1800 1600 1400 1200 | 1000! = 800 600 Wavenumber (em) Figure S11, FTIR spectra for LMOF-261 and LMOF-263. Black labels are used to identify peaks related to the sulfone and other sulfur related moieties (LMOP-263), while blue labels show peaks concerning the car- bonyl group (LMOF-261). ‘The vibrational modes at 1311 (S=O str), 1170 (S=O str), 1133 (SO2 sym), 877 and 854 (C-S st) and 735 em’ (C-S-C) are associated with the presence of the sulfone moeity in LMOF-263 (Figure S11, red). LMOF- 261 contains the carbonyl group in place of the sulfone moeity, characterized by vibrational modes at 1720 (C=0 ste), 1090 (C-O sts), 980 (C-O ste) and 940 em" (C-O stz) (Figure $11, green).°° $9, X-ray Photoelectron Spectroscopy X-ray photoelectron spectroscopy (XPS) was employed to further investigate the interaction of Hg” or Mg".with LMOF-263. Information regarding changes in local electronic structure of S,C and O as a function of Hg” or Mg can be inferred by monitoring the sulfur and oxygen binding energies in LMOF-263. The samples were loaded on a KBr pellet (same procedure as in FTIR), using a Perkin Elmer PHI system equipped with a concentric hemispherical analyzer. An Al Kal (1486.6 €V) monochromatic X-ray source at a chamber base pressure of <1.0 n'Torr was used to excite photoelectrons. Since LMOF-263 is insulating, potential charging was corrected by using a neutralizing flood gun and also insuring that the C Is core level is at 285.4 eV and correcting the other core levels accordingly. Figures $12-S17 display the XPS spectra for pristine and Hg” loaded LMOF-263 samples for vatious Hg" concentrations. ‘The binding energies of carbon (1s), oxygen (1s), sulfur (2p", 2p") and mercury (4f"7, 4°) are noted in the spectra. Figure $18 exhibits the XPS spectra of LMOF-263 exposed to 20,000 ppm Mg”. Sis2 ea aT S 2p%? eH s 2p: 1a se ar Bincing Every eV) Figure $12. X PS spectra for as-made L MOF-263. Cts 2 ais aha an aa Ph abo ‘Binding Energy (eV) $ 2p% S2pi? sto 962 aes Wee a ate Tr Binding Energy (eV) O1s ‘sad 533.7 ‘ning Errey et a Binding Eneroy eV) O1s IB os oe oi oe a oo 68 Binding Energy (eV) ma Se We abs abe in ta ‘Binding Energy iV) Figure $13. XPS spectra of LMOF-263 exposed to water (no Hg) as reference. No trace Hg” is detected after the water treatment throughout the analysis. S16Cis r 2a 285 28821 aba 77900 Binding Ereay(@¥) 5 oe GH ease So oe Binding Energy (eV) Hg 4f"2 S 2p%2 S 2p? eee ehh ae a7 8 ee te ae ‘inding Energy e¥) Binding Energy eV) Figure $14, XPS spectra of LMOF-263 exposed to 100 ppm Hy. Cis O1s ‘Binding Energy (eV) S 2p3? S 2p? 150 162058 a tha 7 Go 2105 08 1H) aia Binding energy (eV) Binding Eneray (eV) Figure S15. XPS spectra of LMOF-263 exposed to 1,000 ppm Hg" Si7Cts Pia 252821 27a 300 ‘Binding Energy (eV) fe 12s eh i a Binding Energy eV) ca a a Binaing Energy (eV) ete ae ain tle Binding Eneroy (eV) Figure $16, XPS spectra of LMOF-263 exposed to 10,000 ppm Hg” Cis 2854 180162 105 ee an aha a7 Binding Eneray (eV) O1s ss asi Os Binaing Energy (eV) Hg 442 Hg 4f82 1033 Seas ee a Binding Eneray (eV) Figure S17. XPS spectra of LMOF-263 exposed to 30,000 ppm Hg" S18Cts O1s se | aia a2 38s 28 a7 Binding Energy eV}. os leo eas Bo Binding Energy (eV) Mg2p 'S 2p? [ S 2p? ie ei Tie ae ining Energy (\ “ainding Energy eV) Figure S18, XPS spectra of LMOF-263 exposed to 20,000 ppm Mg”. The sulfur ($ oxbitals 2p", 2p!) binding energies increase with increased exposure to Hg". In Figures $12 and $13, the carbon, oxygen and sulfur binding energies are the same in both the as-made LMOF-263 and the water-exposed LMOF-263, This confirms that any perturbation in the observed binding energies must be from interactions with Hg”, as shown in Figures $14-S17. A secondary oxygen binding energy (532.9/532.8 €V) is measured in the Hg*-exposed samples that was not observed in the as-made, water-exposed or Mg?- exposed samples. This lends evidence that suggests that the oxygen atom within the sulfone group is also affected by the presence of Hg”. In contrast, upon LMOF-263 exposure to 20,000 ppm of Mg” (Figure S18), there are no changes in the sulfur or oxygen binding energies, supporting the observation that LMOF- 263 selectively interacts with heavy metals. Table S4 summarizes the data from Figures $12-S18. ‘The increase in sulfur binding energy as Hg”* concentration increases is most clearly seen and monitored by overlaying the S core levels in Figure $19. “Table $4. Summary of XPS data for LMOF-263 exposed to various Hg"* and Mg”* concentrations. Binding Energy (eV) G ° 8 Hg/Mg ‘As-made 285.4 5314 168/169 0 H,0 exposed (285.4 ee 168/169 0 100 ppm Hg” 531.5/532.9 168.1/169.24 99.74/103.69 1,000 ppm Hg” (285.4 531.5/532.9 168.15/ 169.28 99.7/103.75, S1910,000 ppm Hg"* 531.5/532.8 168.22/169.3, 99.7/103.62 30,000 ppm Hg” 531.5/532.8 168.3/169.4 99.8/103.8 20,000 ppm Mg** 531.5 168/169 0 — LMOF-263 as-made — LMOF-263 H,0 exposed — LMOF-263 100 ppm Hg” — LMOF-283 1,000 ppm Hg — LMOF-263 10,000 ppm Hg? ~— LMOF-263 30,000 ppm Hg S 2p 166 «167 «168 «169 170) «171 172 Binding energy (eV) Figure $19, Overlayed XPS spectra of LMOF-263 exposed to incremental Hg concentrations, The sulfur binding energy increases (curves shift to the right) when exposed to higher Hg" concentrations. “Table $5 exhibits the change in the oxygen binding energies as Hg" concentration increases. ‘The gradual change indicates that Hg” directly interacts with oxygen atoms in the sulfone moeity. Oxygen atoms drain clectron density from the S-O bond, increasing the ability for Hg” to interact with the outer oxygen atoms, Effective interaction between Hg?" and oxygen atoms within the sulfone group would still prompt indirect electronic changes in the sulfur atom, indicated by the shift in sulfur 2p" and 2p" binding energies. Upon Mg” exposure, the secondary oxygen binding energy peak is nonexistent, emphasizing minimal interactions between the sulfone group and the light metal ‘Table $5. The percent atomic concentration at each oxygen core level over multiple Hg” and Mg” exposure conditions. (02 Binding Energy (eV) ~531.5 ~534 Percent Atomic Concentration (%) Oppm Hg” 7 3 100 ppm He”* 87 13 1,000 ppm Hg” 1 9 10,000 ppm Hg* 722 207 30,000 ppm He* 683 317 20,000 ppm Mg** 100 0 $20A shift to higher sulfur binding energies and the change in the oxygen binding energies with increased Hg” concentration indicate that Hg” is directly interacting with the sulfone moeity. The Hg" ions have a stronger affinity to oxygen compared to sulfur atoms due to the new binding energy peak upon Hg”* exposure relative to the oxygen binding energies measured in as-made LMOF-263 (no Hg” exposure). Additionally, the sulfur binding energies are increasing with elevated Hy" exposure due to electronic changes in the S-O bond, te- sulting from oxygen atoms interacting with Hg”. Similar binding energies for Hg-S interactions have been reported in the literature.* In conclusion, XPS confirms the selective interaction of Hg"* with sulfone groups within LMOF-263, sup- porting conclusions from fluorescence titrations and ICP-OES measurements. S10. Stern-Volmer Curves for Hg™* and Pb* ‘The Stern-Volmer equation was used to determine the quenching efficiency Hg and Pb” in aqueous solution, Stern-Volmer curves are linear at low concentrations, allowing the quench- ing efficiency (Ks) to be calculated from the slope of the line. Jo Tait KslQ) Equation $3, Stern-Volmer Equation: In is the initial fluorescence intensity (before analyte exposure), Tis the fluorescence intensity ata given concentration of analyte, Kyy is the quenching efficiency (Stern-Volmer con- stant) and Q is the concentration of analyte. ‘To compare the effects of different functional groups on the dicarboxylate linkers, LMOF-261, -262 and 263 were exposed to various Hg™ concentrations (following fluorescence titration procedures). Figure $20 shows the Stern-Volmer curves for each member of the isoreticular series, LMOF-263, which contains the sulfone functional group, was quenched more efficiently compared to its counterparts, LMOF-261 and -262 contain carbonyl and methylene groups, respectively, on the central position of the dicarboxylate linker. ‘The: mocities don’t interact as effectively with Hg” compared to the sulfone group. . 7 = LMOF-261 . SLMOF-262 5 {| SLM0F-263 ° 5 es Metal Concentration (uM) Figure $20. Stera-Volmer curves for LMO! titrations, 261, -262 and -263 after exposure to Hg” through fluorescence $21Stern-Volmer curves for Hg" and Pb" detection in LMOF-263 are given in Figure $21, The quenching efficiencies (Ksy) for Hg” and Pb** were 459,446 and 55,017 M", respectively, represented as the slope in the inset equations. 15 og (0.0E+00 206-07 406-07 6.0E07 806-07 1.06.06 1.26.06 a Metal Concentration (M) y=550tTe+1 R= 0.9635 " gu 13 1 ae O0E00 S0EGe 600s watoe 12E08 18k08 b Metal Concentration (M) Figure $21, Stern-Volmer curves for LMOF-263 when exposed to a) Hg” and b) Pb**. Error bars indicate the average standard deviation of 1,/I values between multiple trials of each metal ion S11. Limit of Detection for Hg”* and Pb** When monitoring detection properties in terms of PL quenching, the limit of detection was defined as the concentration of metal ion at which the decrease in intensity was greater than the average standard deviation in repeated measurements of the same sample, The average standard deviations in intensity for the Hg” and Pb* exposures were 1.811 a.u, and 1.799 a. respectively. Using the S-V curves in Figure S21ab we deter- mined the limit of detection for Hg” and Pb" to be 3.3 and 19.7 ppb. To confirm this detection limit, Figure $22 displays a low-concentration titration of LMOP-263 with aqueous solutions of Hg’. The addition of 5 ppb was clearly detected, $2‘400 0 00 ‘so 00 Wavelength (nm) Figure $22. Emission spectra from the low concentration fluorescence titration of LMOP-263 with aliquots of Hg solution, with enhanced detail provided in the inset. $12. References 1. Takashima, 1; Kinoshita, Ms Kawagoe, Rs Nakagawa, S Sugimoto, M.; Hamachi, 1. 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