Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers. This journal is © the Partner Organisations 2023 Electronic Supplementary Information Facile, fast and green synthesis of a highly porous calcium- syringate bioMOF with intriguing triple bioactivity Albert Rosado,*a Oriol Vallcorba,b Blanca Vázquez-Lasa,c,d Luis García-Fernández,c,d Rosa Ana Ramírez-Jiménez,c,d María Rosa Aguilar,c,d Ana M. López-Periago,a Concepción Domingo*a and José A. Ayllón*e a Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, Campus UAB s/n, 08193 Bellaterra, Spain. Email: arosado@icmab.es, conchi@icmab.es b ALBA Synchrotron Light Source, Carrer de la Llum, 2, 26, 08290 Cerdanyola del Vallés, Barcelona, Spain. c Instituto de Ciencia y Tecnología de Polímeros, ICTP-CSIC, C/ Juan de la Cierva, 3, 28006 Madrid, Spain. d Networking Biomedical Research Centre in Bioengineering, Biomaterials and Nanomedicine, CIBER-BBN, Av. Mon-forte de Lemos, 3-5, 28029 Madrid, Spain. e Universitat Autònoma de Barcelona, UAB, Campus UAB s/n, 08193 Bellaterra, Spain. Email: JoseAntonio.Ayllon@uab.es 1 Table of contents Crystalline structure description 3 Figures Figure S1. PXRD pattern of CaSyr-1 nanopowder 5 Figure S2. TEM image of CaSyr-1 nanopowder 5 Figure S3. Particle size distribution histograms of CaSyr-1 nanopowder 6 Figure S4. Particle size distribution under suspension of CaSyr-1 nanopowder 6 Figure S5. Dimeric unit of CaSyr-1 7 Figure S6. Chain formation and interconnection 7 Figure S7. CO2 enthalpy of adsorption of CaSyr-1 8 Figure S8. TGA of CaSyr-1 8 Figure S9. VTPXRD of CaSyr-1 9 Figure S10. Cytotoxicity results of CaSyr-1 and CaSyr-1(ibu) 9 Figure S11. Cytotoxicity results of syringic acid and ibuprofen 10 Figure S12 SEM image of CaSyr-1(ibu) 10 Figure S13. PXRD pattern of CaSyr-1(ibu) nanopowder 11 Figure S14. 1H-NMR of (S)-(+)-ibuprofen 11 Figure S15. 1H-NMR of syringic acid 12 Figure S16. 1H-NMR of CaSyr-1(ibu) 12 Figure S17. 1H-NMR of CaSyr-1(ibu) release after 10 min 13 Figure S18. 1H-NMR of CaSyr-1(ibu) release after 1 hour 13 Figure S19. 1H-NMR of CaSyr-1(ibu) release after 3 hours 14 Figure S20. 1H-NMR of CaSyr-1(ibu) release after 1 day 14 Tables Table S1. Elemental analysis of CaSyr-1 nanopowder 15 Table S2. Calcium-based MOFs tested for CO2 adsorption 15 Table S3. Crystallographic data for CaSyr-1 16 Table S4. Selected bond distances in CaSyr-1 16 Table S5. Selected bond angles in CaSyr-1 17 References 17 2 Crystalline structure description The crystalline structure of CaSyr-1 belongs to the trigonal system with the space group R3̅ (Table S3). The asymmetric unit contains two crystallographically independent Ca2+ ions, two independent Syr2- linkers and two H2O ancillary ligands (Fig. S5). However, both Ca2+ ions show comparable coordination environment and both Syr2- linkers play the same role in the structure (Table S4, S5). Ca1 and Ca2 display a distorted pentagonal bipyramidal geometry, with the typical heptacoordination of calcium. Ca1 and Ca2 are arranged in dimers through a double connection promoted by μ2-oxo (O2 and O5) bridges coming from the deprotonated phenol group in Syr2-. Besides, each Syr2- provides two additional oxygen atoms from the methoxy groups (O1, O3 and O4, O6, respectively), one to each Ca2+, reinforcing the μ2-phenoxo bridges. To rationalize the description of the structure, it is considered that each dimeric subunit is formed by the two Ca2+ and the two Syr2- that are held together through the methoxy-phenolate-methoxy double clamp. The pentagonal plane coordination in the coordination sphere of each calcium is completed by an oxygen (O8 and O10, respectively) coming from a carboxylate group of a syringate that participates in the formation of a neighboring dimeric subunit. Regarding the axial axis, one position is occupied by one aquo ligand (O11 and O12, respectively) and the other by another oxygen atom carboxylate (O7 and O9, respectively) coming from another close binuclear subunit. Hence, each syringate dianion participates in the formation of a dimer by the deprotonated phenol, reinforced by the two adjacent methoxide groups, while interconnecting two other dimeric units of an adjacent chain by an asymmetric μ2-η1: η1 carboxylate bridge. These bridges define chains parallel to the c axis (Fig. S6b), and in each chain the consecutive dimers are related by a center of inversion (Fig. 5d), thus, two different inter-dimer Ca-Ca distances alternate (Ca1···Ca1, d1, and Ca2···Ca2, d2, Fig. S6a). Each chain is connected to four 3 neighbor chains forming two types of prisms, triangular and hexagonal (ratio 2:1) (Fig. S6c), with a disposition in the space that resembles to the Kagome lattice (Fig. S6d). The roughly triangular sections do not display useful porosity according to the measurements in Mercury using a probe radius = 1.2 Å. Contrarily, the hexagonal section displays defined channels of Ø = 14 Å that in the crystal was filled by a disordered mixture of solvents, water and DMF, one molecule of each per calcium atom, so solvent masking strategy was used to refine the crystal structure. Experimental data, particularly powder XRD and N2 adsorption desorption characterization show that the Kagome framework remains intact after solvent elimination and gives rise to a highly porous architecture with a 36 v% of empty void per unit cell volume. 4 Figures Figure S1. PXRD pattern of CaSyr-1 nanopowder prepared in 1 mL of EtOH (1:8 reactants:solvent molar ratio) compared with the simulated pattern from single crystal structural data. Figure S2. TEM image of CaSyr-1 nanopowder prepared in 1 mL of EtOH (1:8 reactants:solvent molar ratio). 5 Figure S3. Particle size distribution histograms measured from the TEM images of CaSyr-1 prepared in 10 mL (green, 1:80 reactants:solvent molar ratio) and 1 mL (blue, (1:8 reactants:solvent molar ratio) of EtOH. Figure S4. Particle size distribution of CaSyr-1 under suspension according to DLS. 6 (a) (b) (c) (d) Figure S5. Dimeric unit of CaSyr-1: (a,b,c) observed from different angles, and (d) center of inversion between the interconnected dimers. (a) (b) (c) (d) Figure S6. Chains formed after dimmer connection in: (a) –{[Ca2Ca1]-[Ca1Ca2]}n- fashion (b), visualized from c axis; (c) chains interconnection forming triangular and hexagonal prisms, and (d) resembling Kagome lattice. 7 Figure S7. CO2 enthalpy of adsorption (Qst) of CaSyr-1. Figure S8. Thermogravimetric analysis of CaSyr-1 under N2. 8 Figure S9. Variable-temperature PXRD (VTPXRD) of CaSyr-1 up to 500 K. Figure S10. Cytotoxicity results of CaSyr-1 and CaSyr-1(ibu). 9 Figure S11. Cytotoxicity results of syringic acid and ibuprofen. Figure S12. SEM image of CaSyr-1(ibu). 10 Figure S13. PXRD pattern of CaSyr-1(ibu) nanopowder compared to CaSyr-1 nanopowder (1:80 reactants:EtOH molar ratio) and the simulated pattern from single crystal structural data. Figure S14. 1H-NMR of (S)-(+)-ibuprofen. 11 Figure S15. 1H-NMR of syringic acid. Figure S16. 1H-NMR of CaSyr-1(ibu) after HF treatment and filtration. 12 Figure S17. 1H-NMR of CaSyr-1(ibu) release after 10 min of exposure to PBS medium. Figure S18. 1H-NMR of CaSyr-1(ibu) release after 1 hour of exposure to PBS medium. 13 Figure S19. 1H-NMR of CaSyr-1(ibu) release after 3 hour of exposure to PBS medium. Figure S20. 1H-NMR of CaSyr-1(ibu) release after 1 day of exposure to PBS medium. 14 Tables Table S1. Elemental analysis of CaSyr-1 obtained in the synthesis performed with 1:80 reactantsts:solvent molar ratio. Material Calculated [%] Experimental [%] Ratio Carbon Hydrogen Carbon Hydrogen Ca:Syr:H2O CaSyr-1 42.52 3.96 42.19 3.92 1:1:1 Table S2. Calcium-based MOFs tested for CO2 adsorption. Ca-based MOF CO2 uptake Conditions Reference [mmolg-1] T [K] / P [kPa] 3.7 273 / 100 CaSyr-1 2.4 298 / 100 This work 1.8 313 / 100 Ca-5TIA-MOF 1.12 298 / 100 S1 MUT-1 0.97 298 / 100 S2 CaBTB 1.98 298 / 100 S3 Ca(SDB) 1.04 273 / 100 S4 15 Table S3. Crystallographic data for CaSyr-1 determined by single crystal XRD. Empirical formulae C18 H20 Ca2 O12 [2(H2 O) 2(C3 H7 N O)] Formula weight 690.72 T [K] 100(2) Wavelength [Å] 0.72932 System, space group Trigonal, R3̅ a [Å] 30.963(2) b [Å] 30.963(2) c [Å] 16.953(1) α [º] 90 β [º] 90 γ [º] 120 V [Å3] 14075(2) Z 18 Dcalc [g cm-3] 1.467 μ [mm-1] 0.469 F(000) 6552.0 Crystal size [mm3] 42 hkl ranges -42≤h≤42 -42≤k≤42 -23≤l≤23 2ϴ range [º] 1.458 to 30.427 Reflections collected/unique/[Rint] 83456/8717/[Rint = 0.0390] Completeness 99.4% Refinement method Full matrix least-squares on |F|2 Data/restrains/parameters 8717/ 0 / 295 Goodness of fit (GOF) on |F|2 1.061 Final R indices [I>2σ(I)] R1 = 0.0336, wR2 = 0.1001 R indices (all data) R1 = 0.0360, wR2 = 0.1018 Largest Diff. peak and hole [e Å-3] 0.451 and -0.494 Table S4. Selected bond distances in CaSyr-1. Bond Distance [Å] Ca1-O1 2.649(1) Ca1-O2 2.303(1) Ca1-O4 2.555(1) Ca1-O5 2.343(2) Ca1-O7 2.302(2) Ca1-O8 2.261(1) Ca1-O11 2.388(2) Ca2-O2 2.327(1) Ca2-O3 2.540(1) Ca2-O5 2.308(1) Ca2-O6 2.675(2) Ca2-O9 2.378(2) Ca2-O10 2.273(1) Ca2-O12 2.407(2) 16 Table S5. Selected bond angles in CaSyr-1. Objects Angle [º] O1-Ca1-O2 64.07(4) O2-Ca1-O5 69.58(5) O4-Ca1-O5 65.52(5) O2-Ca2-O3 65.77(4) O2-Ca2-O5 69.79(5) O5-Ca2-O6 63.61(5) Ca1-O2-Ca2 110.28(5) Ca1-O5-Ca2 109.51(6) References S1. A. Mallick, E. M. Schön, T. Panda, K. Sreenivas, D. Díaz, R. Banerjee, Fine-tuning the balance between crystallization and gelation and enhancement of CO2 uptake on functionalized calcium based MOFs and metallogels, J. Mater. Chem., 2012, 22, 14951- 14963. S2. R. K. Alavijeh, K. Akhbari, J. White, Solid−Liquid Conversion and Carbon Dioxide Storage in a CalciumBased Metal−Organic Framework with Micro- and Nanoporous Channels, Cryst. Growth Des., 2019, 19, 7290−7297. S3. K. Noh, N. Ko, H. J. Park, S. Park, J. Kim, Two porous metal–organic frameworks containing zinc–calcium clusters and calcium cluster chains, CrystEngComm, 2014, 16, 8664-8868. S4. D. Banerjee, Z. Zhang, A. M. Plonka, J. Li, J. B. Parise, A Calcium Coordination Framework Having Permanent Porosity and High CO2/N2 Selectivity, Cryst. Growth Des. 2012, 12, 2162−2165. 17