Multivariate MetalâOrganic Frameworks for the Simultaneous Capture

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Multivariate Metal-Organic Frameworks for the Simultaneous Capture of Organic and Inorganic Contaminants from Water Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Marta Viciano-Chumillas, Lucas H. G. Kalinke, Jesus Ferrando-Soria, Donatella Armentano, and Emilio Pardo J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b06250 • Publication Date (Web): 08 Aug 2019 Downloaded from pubs.acs.org on August 8, 2019

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Journal of the American Chemical Society

Marta Mon,†,¶ Rosaria Bruno,§,¶ Estefania Tiburcio,† Marta Viciano-Chumillas,† Lucas H. G. Kalinke,†,‡ Jesús Ferrando-Soria,*,† Donatella Armentano*,§ and Emilio Pardo*,† †Instituto

de Ciencia Molecular (ICMol), Universidad de Valencia, 46980 Paterna, Valencia, Spain §Dipartimento di Chimica e Tecnologie Chimiche (CTC), Università della Calabria, Rende 87036, Cosenza, Italy ‡Instituto

Federal de Goiás−IFG, 75131-457, Anápolis, Goiás, Brazil

¶These two authors have equally contributed to this work.

ABSTRACT: We report a new water-stable multivariate (MTV) Metal-Organic Framework (MOF) prepared by combining two different oxamide-based metalloligands derived from the natural amino acids L-serine and L-methionine. This unique material features hexagonal channels decorated with two types of flexible and functional “arms” (–CH2OH and – CH2CH2SCH3) capable to act, synergistically, for the simultaneous and efficient removal of both inorganic (heavy metals like Hg2+, Pb2+ and Tl+) and organic (dyes such as Pyronin Y, Auramine O, Brilliant Green and Methylene Blue) contaminants and, in addition, this MTV-MOF is completely reusable. Single-crystal X-ray diffraction (SCXRD) measurements allowed to solve the crystal structure of a host-guest adsorbate, containing both HgCl2 and Methylene Blue, and offered unprecedented snapshots about this unique dual capture process. This is the very first time that a MOF can be used for the removal of all sorts of pollutants from water resources, thus opening new perspectives for this emerging type of MTV-MOFs.

Human presence on the Earth's surface –especially since the Industrial Age– has had a very negative impact on natural aquatic ecosystems, seriously threatening water resources.1 As a consequence, about half of world population have no easy access to clean fresh drinking water.2 Water contamination is one of the main environmental issues humankind is nowadays facing and directly threatens the planet’s environmental balance and sustainability of life on Earth for future generations.3 Contamination sources are manifold, scattered and widely diverse,4 ranging from accidental unauthorized or deliberate industrial dumping to daily human activities such as the consumption and excretion of pharmaceutical products.5 In this context, it becomes clear that the development of novel and efficient methods for water remediation is a pressing need. Among the variety of existing technologies, advanced oxidation processes6 (AOPs) and the adsorption of the contaminant by porous materials7 are particularly promising methodologies. However, they also have certain drawbacks/limitations. For example, the use of AOPs may lead to the generation of secondary pollutants,6 and, the design of a porous material capable to adsorb simultaneously, in an efficient manner, the wide variety of organic and inorganic contaminants has not yet been achieved.8 Amongst the different porous materials with potential application in water remediation, a type of crystalline organic-inorganic hybrid compounds, named MetalOrganic Frameworks9–12 (MOFs), have strongly burst into the environmental remediation scenario.13 MOFs have shown very good performances in the removal of both

inorganic14 and organic15 pollutants, although separately. One of the main reasons for this increasing use of MOFs in this particular field is the ease with which their channels can be pre- or postsynthetically16,17 fine-tuned –in terms of size, shape and functionality–, resulting into a fascinating controlled host-guest chemistry.18–25 In addition, unlike other porous materials, MOFs allow for the use of X-ray crystallography to observe what actually happens within their channels.26–33 Either way, even if MOFs, as said above, have already shown good performances in the capture of hazardous heavy metals,34–37 oxyanions,38,39 nuclear wastes40,41 and organic molecules like organic dyes,42 pharmaceutical products43 or different industrial wastes,44 more work still needs to be done to obtain MOFs with the dual ability to capture both organic and inorganic contaminants at once. This, eventually, would lead to develop more efficient water reclamation protocols and pave the way to move toward the re-establishment of Earth ecosystem balance. Recently,45 an original approach –consisting, basically, of using different types of organic linkers– has emerged for the fabrication of isoreticular MOFs with different and controlled functionalities within their channels. This type of sequence-dependent materials,46 so called multicomponent47–49 or multivariate50–57 (MTV) MOFs, are capable of new functions without apparent loss of synthetic control. Such modular nature of MTV-MOFs, open up vast possibilities in the field of water remediation, as make possible to tailor their porosity with two or more different and cooperative functional groups capable to act synergistically to capture contaminants of very different nature at once.

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Despite these possibilities, no examples of MTV-MOFs with environmental applications have been reported so far.

Here, we present our work, based on our previous experience with oxamide-based metalloligands derived from natural amino acids –which allowed us to obtain a family of water-stable highly crystalline three-dimensional (3D) isoreticular MOFs– featuring functional channels whose functionality depended on the nature of the amino acid residue (Figure S1). The previously reported MOF of formula {CaIICuII6[(S,S)-methox]3(OH)2(H2O)} . 16H2O (1a) (where methox = bis[(S)-methionine]oxalyl diamide), prepared using a metalloligand derived from the Lmethionine amino acid and whose pores were decorated with thio-ether groups (Figure S1a), showed excellent performances in the removal of HgCl2 from water36,37 due to the well-known affinity of sulphur by soft metals. In turn, the MOF prepared with the metalloligand derived from the amino acid L-serine, with formula {CaIICuII6[(S,S)serimox]3(OH)2(H2O)} . 39H2O (1b) (where serimox = bis[(S)-serine]oxalyl diamide), featured functional channels decorated with hydroxyl (–OH) groups (Figure S1b) and exhibited very good capabilities for the capture of organic dyes,58 and other organic molecules,26 establishing weak host-guest interactions. On this basis, we have focused our efforts on the rational design of a MTV-MOF prepared from the combination of two different kinds of oxamato-based metalloligands derived from amino acids. Thus, we report here, a novel isoreticular MOF of formula {CaIICuII6[(S,S)-methox]1.43-1.46(S,S)-serimox]1.571.54(OH)2(H2O)} . 30H2O (2) together with the isostructural compound of formula {BaIICuII6[(S,S)-methox]1.41-1.45(S,S)serimox]1.59-1.55(OH)2(H2O)} . 31H2O (2’) (see Supporting Information) featuring medium-sized (ca. 0.9 nm) functional channels decorated, with approximately, a 50 % of hydroxyl-containing groups (–CH2OH) derived from the natural amino acid L-serine and a 50 % of thio-alkyl (– CH2CH2SCH3) groups derived from the natural amino acid L-serine (Figures 1, 2 and S1c).

Figure 1. Perspective view of the open-framework of MTV– MOF 2 along the c axis (the crystallization water molecules are omitted for clarity). Ligands and metal atoms from the network are depicted as gray stick with the exception of the Lserine (–CH2OH) and L-methionine (–CH2CH2SCH3) residues, which are represented as red and yellow sticks, respectively. Oxygen and sulphur atoms from the residues are shown as red and yellow spheres, respectively.

Well-shaped crystals of compound 2 (and 2’) were grown with a slow diffusion technique and the crystal structure of 2 was determined by single-crystal X-ray diffraction (SCXRD) (see Supporting Information details). 2 crystallizes in the chiral P63 space group and its structure consists of uni-nodal acs six-connected 3D calcium(II)copper(II) networks featuring functional hexagonal channels, where both types of flexible amino acid residues, the hydroxymethyl (–CH2OH) and the ethylenethiomethyl (– CH2CH2SCH3) chains of the serine and methionine, respectively coexist (Figures 1, 2 and S1c-S3).

Figure 2. (a) Fragment of the structure of 2 emphasizing the dicopper(II) building block. Views of a single channel for the porous structure of the MTV–MOF 2 along the c (b) and a (c) axes (the crystallization water molecules are omitted for clarity). The flexible amino acid –CH2OH and –CH2CH2SCH3 residues exhibit a statistical disorder (with 1:1 ratio). For the sake of clarity here is represented the crystal structure solved with superimposed snapshot of mixed {CuII2[(S,S)-methox/serimox]}. Further details in text and Scheme S2 in SI. Copper(II) and calcium(II) ions from the network are represented as cyan and purple spheres, respectively. Oxygen and sulphur atoms from the residues are shown as red and yellow spheres, respectively. The organic ligands are represented as sticks with the following color scheme: sulphur, yellow; oxygen, red; nitrogen, light blue; carbon, gray, with the exception of L-serine (–CH2OH) and L-methionine (–CH2CH2SCH3) residues, which are represented as red and yellow sticks, respectively.


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The flexible amino acid derivative chains remain confined and stabilized, by lattice water molecules, in the highly hydrophilic pores of the MOF (Figures 1, 2 and S1S3). This mixed-ligand structure is still highly porous –the channels size being similar to that of the single-ligand parent compound serimox (1b) and higher to that of the other single-ligand parent compound methox (1a) (Figure S1). This uni-nodal acs six-connected net is built up from trans oxamidato-bridged dicopper(II) units of {CuII2[(S,S)serimox]} and {CuII2[(S,S)-methox]} (Scheme S1 and Figure S1c), which are statistically disordered in the crystal structure. In order to examine such statistical disordered in depth, we performed SCXRD measurements –using synchrotron radiation at the I19 beamline of the Diamond Light Source– on the highest quality crystals of sample 2’. Despite the quality of data set measured up to theta 36° (see Supporting Information and Table S1), no appreciable variations in final model of crystal structure was observed (see Figures S4-S5). Undoubtedly the most ‘realistic’ situation within crystals of these MTV-MOFs is, of course, a random distribution of serine and methionine moieties (with 1:1 ratio) within the net (see Crystallographic details in Supporting Information, Scheme S2 for an alternative way to solve 2’ crystal structure). Most likely, the very similar percentage of serimox and methox leads to superimposed snapshot of mixed {CuII2[(S,S)-methox/serimox]} metalloligands further confirming the composition analysis (vide infra C, H, S, N and Supporting Information). This disorder gives an averaged view of 2 with a crystal structure that is, of course, the spatial average, of all molecules/fragments, together with all their possible orientations averaged, in the crystal via only one unit-cell (see Crystallographic details in the Supporting Information). In 2, as in the parent compounds 1a and 1b copper(II) dimers act as linkers between the CaII ions (or Ba2+ for 2’) through the carboxylate groups (Figure S1b). Aqua/hydroxo groups (in a 1:2 statistical distribution) further interconnect neighboring Cu2+ and Cu2+/Ca2+ ions whose result linked in a 3 fashion (Figures S1c and S3). C, H, S, N analyses further confirmed the chemical identity of 2 (and 2’) determined by single-crystal X-ray diffraction (See Experimental Section in Supporting Information). The experimental powder X-ray diffraction (PXRD) patterns of polycrystalline samples of 2 (and 2’) fit well with the theoretical ones (Figure S6), confirming the homogeneity of the bulk samples and their isostructurality with the crystals selected for single-crystal X-ray diffraction. The water contents of 2 and 2’ (and also (MB)·HgCl2@2, vide infra) were estimated by thermogravimetric analysis (TGA, Figure S7). The permanent porosities of 2 and 2’ were verified by measuring their N2 adsorption isotherms at 77 K (Figure S8). The calculated Brunauer-EmmettTeller (BET) surface areas59 for 2 and 2’ are 659 and 647 m2/g, respectively –falling between those observed for 1a (126 m2/g) and 1b (828 m2/g) but closer to the last one– which agrees well with the pore size observed in the crystal structure. The reported analyses from the bulk and individual crystal sample of 2 showed that the obtained MTV-MOF had a ligand ratio composition similar to that present in the reaction mixture. Thus demonstrating that there were no significant ligand preferences and that the

composition can be controlled through the relative reactant concentrations. The porous nature of 2 together with the fact that its channels are decorated with two different types of functional groups, with already proven affinity for inorganic – soft heavy metals–27,31,37,60 and organic contaminants – dyes, vitamins, drugs–26,58 encouraged us to evaluate its applicability in the simultaneous removal of both organic dyes and heavy metals from water.

Figure 3. (a) Kinetic profile of the removal of Pyronin Y (PY), Auramine O (AO), Brilliant green (BG) and Methylene blue (MB) from a multi-dye solution containing 10 ppm of PY, AO, BG and MB in mineral water in the presence of 50 mg of a sample of 2. Data for the preparation of this picture are collected in Table S3. (b) Kinetic profile of the metal capture by MTV-MOF 2 measured as the decrease of the different metal concentration with time after soaking 50 mg of 2 in a 1 ppm aqueous solution of Hg(II), Pb(II), Tl(I), Cu(II), Ni(II), Ca(II), Mg(II), K(I) and Na(I) in the 0-48 h. interval (data collected in Table S4). The graph only shows the 0-360 min. interval.

First, on the basis of our previous results with the serine-derived MOF 1b –which featured functional channels densely decorated with the highly flexible L-serine residues containing hydroxyl groups leading to an efficient removal of organic dyes58– we now explored the removal of the same dyes by the MTV-MOF 2 which contains ca. a 50% of the hydroxyl groups of 1b together with another 50% of thioalkyl groups from the L-methione ligands. For that, we planned four individual experiments, in which 50 mg of a polycrystalline sample of 2 were soaked, inde-



pendently, in four aqueous solutions of each dye (10 ppm, 20 mL). The dyes uptake was estimated, through UV-vis spectroscopy measurements,58 at specific time intervals (Figure S9) and a kinetic profile of the process was extracted (Table S2 and Figure S10). The adsorption of all four dyes occurs in a very efficient and fast manner about 90% of all four dyes is removed after only 15 minutes (ca. 98% after 24 hours). Another similar uptake experiment was then carried out in a contaminated multi-dye aqueous solution containing 10 ppm of PY, AO, BG and MB, in order to confirm that this MOF is capable to kidnap, simultaneously, all organic contaminants (Figure S11). Indeed, 2 was capable to adsorb the four dyes even faster and more efficiently than separately (Table S3 and Figure 3a). These findings are particularly significant considering that such cleansing efficiency is achieved in very diluted conditions, like those found in real industrial wastewaters. Remarkably, both the efficiency and the kinetics of the cleaning process is improved in 2 as compared to MOF 1b. This fact does not only imply that thioether groups also participate in the removal and immobilization of the organic molecule, but also suggests that they do it in a cooperative manner with hydroxyl-containing arms. This has not been observed before in the field. Thereafter, we evaluated the efficiency and selectivity of MTV-MOF 2 towards the selective removal of toxic soft heavy metals –with affinity for thioether group– like Hg(NO3)2, Pb(NO3)2 and TlNO3 from water, in the presence of other innocuous metal salts (see Supporting Information for details). For that, 50 mg of a polycrystalline sample of 2 were soaked in a 1 ppm aqueous solution of Hg(NO3)2, Pb(NO3)2, TlNO3, NaNO3, KNO3, Mg(NO3)2, Ca(NO3)2, Ni(NO3)2 and Cu(NO3)2. The efficiency, as well as the kinetic profile, was determined through ICP-MS and SEM/EDX analyses, by measuring the decrease of the concentration of metal salt at specific time intervals (0-2880 min, Table S4). This experiment indicated that 2 is capable to adsorb Hg(NO3)2, Pb(NO3)2 and TlNO3 very efficiently, quickly and selectively, whereas NaNO3, KNO3, Mg(NO3)2, Ca(NO3)2, Ni(NO3)2 and Cu(NO3)2 were not removed at all (see Table S4 and Figures 3b and S12). These results improve previously reported for methione-derived MOF 1a,37 which show similar efficient results for HgCl2 but with double amount of thioether residues. Overall, the present results indicate that MTV-MOF 2 is capable to clean up, very efficiently (Tables S2-S4), contaminated aqueous solutions by both inorganic and organic pollutants in independent experiments. The obvious next step was to determine if 2 was also capable to decontaminate an aqueous solution containing simultaneously both types of pollutants. To this end, we prepared a 1 ppm aqueous solution of Hg(NO3)2, Pb(NO3)2, TlNO3, NaNO3, KNO3, Mg(NO3)2, Ca(NO3)2, Ni(NO3)2 and Cu(NO3)2 to which 10 ppm of PY, AO, BG and MB were also added. Thereafter, 50 mg of 2 were soaked in the solution under continuous stirring. The dual capture process was followed by the combination of UV-vis spectroscopy with ICP-MS and SEM/EDX analyses and the kinetic profiles were established for both types of contaminants by measuring the decrease of the concentration of each pollutant at specific

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time intervals (Tables S5 and S6 and Figures 4 and S13S15). The present experiments do not only confirm that MTVMOF 2 is capable to capture, simultaneously, highly harmful inorganic species like Hg2+, Pb2+ or Tl+ and organic dyes commonly found in industrial wastewaters. Moreover, the removal efficiencies (Tables S5 and S6) are slightly enhanced in comparison with the independent experiments (Tables S2-S4), which suggest, to a certain extent, a synergetic behavior involving the two types of functional groups acting together for the accommodation and capture of the different types of contaminants. In addition, it was also confirmed that 2 is reusable and that the capture process is reversible. Thus, after the simultaneous capture experiments described above, both types of contaminants were completely extracted from 2 by suspending, consecutively, the loaded material in 2-mercaptoethanol and ethanol for 4 and 2 hours, respectively. The reusability of 2 was confirmed by chemical analyses (see Experimental section and Supporting Information), the PXRD pattern of 2 after the extraction process (Figure S16) and a second adsorption process carried out with the reused material (Tables S7 and S8). The observed results are very similar to those obtained for the first cycle. Finally, in order to confirm the higher efficiency of this MTV-MOF (2), compared to the previously reported MOFs 1a and 1b, we also carried out the same capture experiments by using a mixture of MOF 1a (25 mg) and MOF 1b (25 mg). They show an approximately 15% and 20% worse efficiency for the removal of inorganic and organic contaminants, respectively (see Tables S9 and S10 in the Supporting Information).

Figure 4. Maximum recovery (after 6 h.) of both inorganic [Hg(II), Pb(II), Tl(I), Cu(II), Ni(II), Ca(II), Mg(II), K(I), Na(I)] and organic contaminants (PY, AO, BG and MB) by MTV-MOF 2 (data collected in Tables S5 and S6).

Aiming at obtaining snapshots about the nature of this dual capture process, we soaked crystals of 2 within a saturated aqueous solution containing HgCl2 and Methylene Blue (see experimental section for details). In so doing, we have obtained (MB)·HgCl2{CaIICuII6[(S,S). methox]1.46(S,S)-serimox]1.54(OH)2(H2O)} 6H2O [(MB)·HgCl2@2] adsorbate.


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The crystal structure of (MB)·HgCl2@2, could be determined by single-crystal X-ray diffraction (SCXRD) allowing thus an unprecedented structural visualization on organic/inorganic pollutants interaction as well as on the molecular recognition process involved in the simultaneous capture process of contaminants different in nature (Figures 5, 6 and S17-S20). Indeed, to the best of our knowledge, it is the first crystal structure of an adsorbate with guests of different nature confined together within functional pores. This allows visualizing the accomplished molecules and metal capture and the exceptional structural versatility of the final system. It is worth to note that (MB)·HgCl2@2 crystals were previously measured in a SCXR Diffractometer in synchrotron (in I19 beamline of the Diamond Light Source) with poorest results, most likely due to fast crystal deterioration under synchrotron beam radiation. Bearing in mind that crystal structure of compound (MB)·HgCl2@2 has been obtained measuring on crystals which suffered a single-crystal to single-crystal (SC to SC) process, it is quite reasonable.

Figure 5. Perspective view of a single pore in (MB)·HgCl2@2 adsorbate, along the c axis, showing HgCl2 and MB guest molecules held in the hexagonal nanopores of 2. Color code of the net is as in Figure 1. Mercury(II) and chlorine atoms are depicted as magenta and green spheres. Carbon atoms of organic dyes are depicted as blue or magenta sticks (representing two sets of configurations). N···O and Hg···S interactions are depicted as red and yellow dashed lines respectively. Cl···S between inorganic HgCl2 molecules and organic dyes are depicted as green dashed lines.

Compound (MB)·HgCl2@2 is isomorph to 2 and crystallizes in the P63 chiral space group of the hexagonal system, confirming the preservation of the 3D network of the hosting matrix 2 even after guests’ capture. The crystal structure clearly evidences HgCl2 guest molecules held in the hexagonal nanopores of 2, being recognized by the thioether arms of the methionine residues and stabilized into the channels through S···Hg interactions, together with MB molecules (Figure 5 and S18-S19). Even though the MB molecules were persistently disordered in the pores, we succeeded to get their possible configurations and loca-

tions by SCXRD (see SI for structural details) and even their interaction sites with both MTV-MOF hosting matrix and HgCl2 molecules –sharing pores with them (Figure 6). MB molecules reside in the pores, packed via hydrogen bond interactions, mediated by serine derivative arms (Figures 5, 6 and S17-S18) and direct S···Cl interactions with inorganic pollutants (Figure 6).

Figure 6. Details of host-guest interactions in (MB)·HgCl2@2. Spot of H-bonds involving serine residue hydroxyl groups anchoring nitrogen atoms of Methylene Blue moieties [N···O distance 3.10 Å] (red dotted lines). Copper and calcium are represented by green and blue spheres respectively, whereas the ligands and guest molecules are depicted as grey and skyblue sticks for carbon and nitrogen respectively. Mercury(II) and chlorine atoms are depicted as magenta and green spheres. L-serine (–CH2OH) and L-methionine (–CH2CH2SCH3) residues, are represented as red and yellow sticks, respectively. N···O and Hg···S are depicted as red and yellow dashed lines respectively whereas Cl···S between inorganic HgCl2 molecules and organic dyes are depicted as green dashed lines.

An in depth analysis of the (MB)·HgCl2@2 crystal structure unveils methylene blue molecules (statistically disordered on two configuration sets, see Figures 6 and S17) packed via H-bonds involving hydroxyl groups of serine moieties and nitrogen atoms of dye molecules [N···O distances of 3.097(6) Å] (Figure S18). On the contrary, HgCl2 molecules are captured via methionine residues, which involve sulphur atoms to bind Hg2+ with a distance of 2.810 (7) Å, (Figure 6), in agreement with those found in the literature.36,37 The arrangement of HgCl2 molecules leave channels still largely porous to confine organic dyes (Figure S20). Indeed, there are interactions between inorganic and organic pollutants and thus, S···Cl contacts with a distance of 2.996(8) Å can be observed (Figure 6). These direct contacts between guests have the two-fold result of imposing preferential configurations and a high degree of loading for guests, which displace almost all water molecules from pores. We consider, this is at the origin of final properties of adsorbate, which shows a pronounced ro-



bustness, being stable at room temperature for weeks, thus ensuring a more safely storage and handling of a material, that releases pollutants only in the appropriate solvent during the regeneration process.

In summary, we have reported a novel MTV-MOF, which was specifically designed –by tailoring its channels with – CH2CH2SCH3 and –CH2OH “arms”– for the simultaneous dual removal of inorganic and organic pollutants like heavy metals and organic dyes from water in a very fast, effective, selective and synergistic manner, as thermodynamic/kinetic sorption studies and SCXRD methods evidence. The present results, do not only constitute the first example of MTV-MOFs with application in environmental remediation, but the first structural visualization of organic/inorganic pollutants involved in the simultaneous capture process as well. Moreover, this is the very first time that a MOF can be used for the removal of all sorts of pollutants from water resources at once. These results further expand the range of applications of MTV-MOFs. In this sense, more work it is being pursued in our research group to conscientiously explored it.

Preparation of {CaIICuII6[(S,S)-methox]1.43-1.46(S,S)serimox]1.57-1.54(OH)2(H2O)} . 30H2O (2) {BaIICuII6[(S,S)methox]1.41-1.45(S,S)-serimox]1.59-1.55(OH)2(H2O)} . 31H2O (2’): Well-shaped hexagonal prisms of 2 and 2’ suitable for SCXRD were obtained by slow diffusion in H-shaped tubes of aqueous solutions containing stoichiometric amounts of (Me4N)2{Cu2[(S,S)-serimox](OH)2} . 5H2O (0.119 g, 0.18 mmol) and (Me4N)2{Cu2[(S,S)-methox](OH)2} . 4H2O (0.131 g, 0.18 mmol) in one arm and CaCl2 . 2H2O (0.018 g, 0.12 mmol) or BaCl2 . 2H2O (0.029 g, 0.12 mmol) in the other. They were isolated by filtration on paper and airdried. Anal. calcd for 2: C29.84Cu6CaS2.92H99.68N6O54.08 (1923.2): C, 18.64; H, 5.22; S, 4.87; N, 4.37%. Found: C, 18.66; H, 5.20; S, 4.88; N, 4.36%; IR (KBr): ν = 1613 and 1608 cm–1 (C=O). C, H, N, S, analyses gave a final formula of {CaIICuII6[(S,S)-methox]1.46(S,S)-serimox]1.54(OH)2(H2O)} . 30H2O. Anal. calcd for 2’: C29.8Cu6BaS2.90H101.6N6O55.10 (2037.53): C, 17.57; H, 5.03; S, 4.56; N, 4.12%. Found: C, 17.59; H, 5.01; S, 4.55; N, 4.14%; IR (KBr): ν = 1611 and 1606 cm–1 (C=O). C, H, N, S, analyses gave a final formula of {BaIICuII6[(S,S)-methox]1.45(S,S)-serimox]1.55(OH)2(H2O)} . 31H2O. A gram-scale procedure was also carried out successfully by mixing greater amounts of (Me4N)2{Cu2[(S,S)serimox](OH)2} . 5H2O (2.375 g, 3.60 mmol) and (Me4N)2{Cu2[(S,S)-methox](OH)2} . 4H2O (2.621 g, 3.60 mmol) in water (40 mL). Another aqueous solution of CaCl2 . 2H2O (0.176 g, 1.20 mmol) was added dropwise to the resulting deep green solution and the final mix was allowed to react, under stirring, for 6 hours. Afterwards, the material was isolated by filtration and characterized by C, H, N, S, analyses to give a final formula of {CaIICuII6[(S,S)methox]1.43(S,S)-serimox]1.57(OH)2(H2O)} . 30H2O (2). Yield: 2.00 g, 87%; Anal.: calcd for C29.72Cu6CaS2.86H99.44N6O54.14 (1920.5): C, 18.59; H, 5.22; S, 4.78; N, 4.38%. Found: C, 18.58; H, 5.19; S, 4.77; N, 4.39%;

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IR (KBr): ν = 1611 and 1609 cm–1 (C=O). The same procedure was repeated by using BaCl2 . 2H2O (0.293 g, 1.20 mmol) instead of CaCl2 . 2H2O and another material was isolated by filtration and characterized by C, H, N, S, analyses to give a final formula of {Ba IICuII6[(S,S)methox]1.41(S,S)-serimox]1.59(OH)2(H2O)} . 31H2O (2’). Yield: 2.22 g, 91%; Anal.: calcd for C29.64Cu6BaS2.82H101.28N6O55.18 (2034.0): C, 17.50; H, 5.02; S, 4.45; N, 4.13%. Found: C, 17.48; H, 4.97; S, 4.44; N, 4.14%; IR (KBr): ν = 1614 and 1611 cm–1 (C=O). Preparation of (MB)·HgCl2{CaIICuII6[(S,S). methox]1.46(S,S)-serimox]1.54(OH)2(H2O)} 6H2O [(MB)·HgCl2@2]: Well-shaped hexagonal prisms of (MB)·HgCl2@2, suitable for SCXRD, could be obtained by soaking crystals of 2 (5.0 mg) for a week in saturated aqueous solutions containing methylene blue and HgCl2 salt (recharging fresh saturated solutions daily). After this period, they were isolated by filtration, air-dried and characterized by C, H, N, S and TGA analyses to give a final formula of (MB)·(HgCl2){CaIICuII6[(S,S)-methox]1.46(S,S)serimox]1.54(OH)2(H2O)} . 6H2O (2). Anal.: calcd for C45.84Cu6CaCl3HgS3.92H69.68N9O30.08 (2082.1): C, 26.44; H, 3.37; S, 6.04; N, 6.05%. Found: C, 26.41; H, 3.33; S, 6.07; N, 6.04%; IR (KBr): ν = 1645 (C=N) and 1607 and 1609 cm–1 (C=O). Capture experiments: Kinetic profile of the capture of the organic dyes: In order to evaluate the kinetics and the efficiency of the capture process, 50 mg of a polycrystalline sample of 2 were soaked in 20 mL of four aqueous solutions containing Pyronin Y (PY), Auramine O (AO), Brilliant Green (BG) and Methylene Blue (MB), respectively (10 ppm, pH ≈ 7.0). Each mixture was stirred at room temperature and the concentration of the supernatant solutions were estimated through UV-vis spectroscopy at different time intervals (see main text). The same experiment was repeated, for each dye individually (Table S2 and Figures S9 and S10) and for a “multi-dye” solution containing 10 ppm of each dye (Table S3 and Figures 3 and S11), in water. Kinetic profile of the capture of the metal salts: In order to evaluate the kinetics of the capture processes (see text), 50 mg of a polycrystalline sample of 2 were soaked in 20 mL of an aqueous solution of Hg(NO3)2, Pb(NO3)2, TlNO3, NaNO3, KNO3, Mg(NO3)2, Ca(NO3)2, Ni(NO3)2 and Cu(NO3)2 (1 ppm, pH ≈ 7.0). The mixture was stirred at room and 200 L aliquots were extracted at different time intervals (see Table S4 and Figures 3 and S12), the cation concentrations being estimated through ICP-MS analyses.

Kinetic profile of the simultaneous capture of the organic dyes and metal salts from the multicomponent solution: 50 mg of a polycrystalline sample of 2 were soaked in 20 mL of an aqueous solution containing 1 ppm of Hg(NO3)2, Pb(NO3)2, TlNO3, NaNO3, KNO3, Mg(NO3)2, Ca(NO3)2, Ni(NO3)2 and Cu(NO3)2 and 10 ppm of PY, AO, BG and MB. The mixture was stirred at room temperature and the concentration of each pollutant was estimated from the supernatant solutions through UV-vis spectroscopy (organic dyes) and ICP-MS analyses (metal salts) at different time intervals (see main text, Tables S5 and S6 and Figures 4 and S13-S15).


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Recycling of 2: After the simultaneous capture experiments described above, both types of contaminants were completely extracted from 2 by suspending, consecutively, the loaded material in 2-mercaptoethanol and ethanol for 4 and 2 hours respectively. The resulting material –with formula {CaIICuII6[(S,S)-methox]1.46(S,S)serimox]1.54(OH)2(H2O)} . 12H2O . 8CH3CH2OH– was characterized by elemental analysis: Anal.: calcd for C45.84Cu6CaS2.92H111.68N6O44.08 (1967.4): C, 27.98; H, 5.72; S, 4.76; N, 4.27%. Found: C, 27.94; H, 5.69; S, 4.79; N, 4.30%. In order to determine the reusability of this material, 50 mg of this recycled polycrystalline sample of 2 were soaked in 20 mL of an aqueous solution containing 1 ppm of Hg(NO3)2, Pb(NO3)2, TlNO3, NaNO3, KNO3, Mg(NO3)2, Ca(NO3)2, Ni(NO3)2 and Cu(NO3)2 and 10 ppm of PY, AO, BG and MB. The mixture was stirred at room temperature and the concentration of each pollutant was estimated from the supernatant solutions through UV-vis spectroscopy (organic dyes) and ICP-MS analyses (metal salts) at different time intervals (see main text, Tables S7 and S8). Kinetic profile of the simultaneous capture of the organic dyes and metal salts from the multicomponent solution by a mixture of 1a and 1b: 50 mg of a mixture of polycrystalline samples of 1a (25 mg) and 1b (25 mg) were soaked in 20 mL of an aqueous solution containing 1 ppm of Hg(NO3)2, Pb(NO3)2, TlNO3, NaNO3, KNO3, Mg(NO3)2, Ca(NO3)2, Ni(NO3)2 and Cu(NO3)2 and 10 ppm of PY, AO, BG and MB. The mixture was stirred at room temperature and the concentration of each pollutant was estimated from the supernatant solutions through UV-vis spectroscopy (organic dyes) and ICP-MS analyses (metal salts) at different time intervals (see main text, Tables S9 and S10). X-ray crystallographic data collection and structure refinement: : Crystals of 2, 2’ and (MB)·HgCl2@2 were selected and mounted on a MITIGEN holder in Paratone oil. Crystals of 2 and 2’ were very quickly placed in a nitrogen stream cooled at 100 K to avoid the possible degradation upon desolvation or exposure to air whereas crystals of (MB)·HgCl2@2 aggregates were measured at 296 K, without displaying any kind of crystal decay, to further test their stability at air and room temperature. Diffraction data for 2’ were collected using synchrotron radiation at I19 beamline of the Diamond Light Source at  = 0.6889 Å, whereas for 2 and (MB)·HgCl2@2 data were acquired on a Bruker-Nonius X8APEXII CCD area detector diffractometer using graphite-monochromated Mo-Kα radiation ( = 0.71073 Å) (see Supporting Information for further details).

Supporting Information Available. Experimental preparation, analytical and spectroscopic characterization. Tables S1-S10, Schemes S1 and S2 and Figures S1-S20. CCDC reference numbers CCDC 1921928-1921930. This material is available free of charge via the Internet at http://pubs.acs.org.

* To whom correspondence should be addressed. E-mail: [email protected]; [email protected]; [email protected]

The authors declare no competing financial interests.

This work was supported by the MINECO (Spain) (Project CTQ2016-75671-P and Excellence Unit “Maria de Maeztu” MDM-2015-0538) and the Ministero dell’Istruzione, dell’Università e della Ricerca (Italy). M. M. and R. B. thank the MINECO and the MIUR (Project PON R&I FSE-FESR 20142020) for predoctoral grants. Thanks are also extended to the Ramón y Cajal Program (E. P.), the “Fondo per il finanziamento delle attività base di ricerca” (D.A.), the “Juan de la Cierva-Incorporación-2017” (J. F.-S.), the “2019 Postdoctoral Junior Leader-Retaining Fellowship, la Caixa Foundation” (J. F.-S.), the Diamond Light Source for awarded beamtime and provision of synchrotron radiation facility and Dr David Allan and Dr Sarah Barnett for their assistance at I19 beamline. E.P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation programme / ERC Grant Agreement No 814804, MOF-reactors.

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