Supplementary information Advances and Challenges in the Creation of Porous Metal Phosphonates Bharadwaj Mysore Ramesha * and Vera Meynen Laboratory for Adsorption and Catalysis (LADCA), Department of Chemistry, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium; [email protected] * Correspondence: [email protected]; Tel.: +32-(0)3-265-23-53 Received: 26 October 2020; Accepted: 24 November 2020; Published: 26 November 2020 Table S1. Synthesis Protocol for Porous Metal Phosphonates. Metal Precursor Phosphonic Linker Synthesis Method Final Morphology References Mono-alkyl Direct precipitation phosphonic acids Lamellar hexagonal ZrOCl2 in HF (aqueous [1] and their dialkyl particles (10–100 μm) media) ester Direct precipitation Th(NO3)4 Mono-terphenyl and in HF Lamellar particles [2] ZrOCl2 bis-terphenylene PA (dioxane/water) α,ω-bis(phosphonic Direct precipitation ZrOCl2 acid) alkyl or aryl Lamellar thin films [3] in HF linker Butane DPA, benzene DPA,bis(phosphono Direct precipitation Lamellar structure ZrOCl2 [4] methyl) DPA, in HF (DMSO/water) with mesoporosity diphenyl DPA with H3PO4 Lamellar structure Zr (IV) fluoro Direct precipitation 3,3’, 5,5’-TMBPDA with inter-layer [5] complexes in HF microporosity Phenyl-DPA Co-condensation in ZnCl2 Lamellar structure [6] Biphenylyl-DPA water Co-condensation in CuSO4 5H2O & Phenyl-DPA and water under reflux or Lamellar structure [7] CuNO3 2.5H2O Biphenylyl-DPA hydrothermal conditions Ethylene-DPA and Co-condensation in CuSO4 5H2O & ZnCl2 Lamellar structure [8] Propylene-DPA water Lamellar particles Benzene DPA + Direct precipitation ZrOCl2 with [9] H3PO4 in HF micro/mesoporosity Bis(methylene) Co-condensation in Zn(NO3)2 & Cd(NO3) Lamellar structure [10] phenyl-PA water Phenyl DPA with Hydrothermal in Lamellar with slit- ZnCl2 [11] H3PO4 water shape pores 6.6 nm Lamellar structure Hydrothermal in with Mn(ac)2 & Zn(ac)2 NMIB-DPA [12] EtOH/water 3D porous framework Co-condensation & 1D polymeric Co(ac)2 Octyl DPA Hydrothermal in network and [13] water (HF) Layered structure Micro and SnCl4 Phenyl PA Hydrothermal in HF [14] mesoporous Hydrothermal in 3D non-porous Sn(CO2)2 Phenyl DPA [15] water layered structure Materials 2020, 13, 5366; doi: 10.3390/ma13235366 www.mdpi.com/journal/materials Materials 2020, 13, 5366 2 of 7 Layered spherical Phenyl PA SnCl4 Hydrothermal in HF globules with [16] Methyl PA micro/mesoporosity Direct precipitation Supermicroporous SnCl4 PPPA followed by [17] layered particles hydrothermal in HF Layered micro and SnCl4 PPPA Direct precipitation mesoporous [18] ZrOCl2 PPA in HF structure Layered nano-sized Phenyl-PA SnCl4 Hydrothermal in HF particles with [19] Biphenyl-PA micro/mesoporosity Small nanoparticles SnCl4 bpyBPAE + Methyl Hydrothermal in (<15 nm) with [20] ZrOCl2 PA DMSO (HF) micro/mesoporosity Abbreviations: PA = Phosphonic acid; DPA = Diphosphonic acid; 3,3’,5,5’-TMBDPA = Tetramethylbiphenyldiphosphonic acid; NMIB = N-methyliminobis(methylenephosphonic acid); PPPA = 4-(4’- phosphonophenoxy)phenyl phosphonic acid; PPA = Phenylphosphonic acid; and bpyBPAE = Tetraethyl 2,2’- bipyridinediyl-5,5’-bis(phosphonate). Table S2. Phosphonate—MOFs. Metal Precursor Phosphonic Linker Synthesis Method Final Morphology References 3D framework with Hydrothermal in Hydrous TiO2 Methylene DPA layered structure— [21] HF/water Non-porous Hexagonal array of CoCl2 & Co(ac)2 Hydrothermal in N,N’-PBMDPA channels with 10 Å [22] NiCl2 & Ni(ac)2 water pores Hydrous TiO2 Hydrothermal in 3D framework with N,N’-PBMDPA [23] AlCl3 HF/water microporosity Co-condensation in 3D porous structure Zn(ClO4)2 DHBP water & reflux with with microporosity [24] DMF (10 Å pores) Open-framework Pb(ac)2 Hydrothermal in EDTP with tunnels & [25] ZnCl2 water/EtOH microporous Hydrothermal in 3D supramolecular Pb(NO3)2 N,N’-PBMDPA [26] water framework Co- condenastion/Precipi ZrOCl2 PBMPA Layered framework [27] tation in water (NH4F or HF) Co-condensation 3D network with Zn(NO3)2 BDPEt [28] (THF/water) channels of ~4.5A° Layered pillar BDPEt Co-condensation CuCl2 structure with VdW [29] BDPMe (EtOH/water) interaction Pillared interlayer BDPA Co-condensation CuCO3·Cu(OH)2 architecture with [30] Amino triazole (MeOH/water) apparent pores Hydrothermal in 3D frameworks with Ni(ac)2 N,N’-PBMDPA [31] water 0.9 nm pores 3D honeycomb Hydrothermal in Co(ac)2 N,N’-BPBMDPA architecture with [32] water pores of 1.8 nm Octaethyl pyrene- 3D framework made Hydrothermal in BaBr2·2H2O 1,3,6,8- up by crosslink of 1D [33] EtOH/water tetraphosphonate chains Hydrothermal in Amorphous SnCl4 BTBP [34] MeOH microporous (~8.5 Å) CuSO4, NiO, NiSO4, BTTMT Hydrothermal in 2D double-layered [35] & MnSO4 TMB-BTTMT water structure with 1D Materials 2020, 13, 5366 3 of 7 tunnel with aperture of 3.5 Å × 7.0 Å ZrOCl2 BTBP Direct precipitation Non-porous [36] in HF honeycomb-like motif ZrOCl2 TTBMP Direct precipitation Permanent [37] in HF microporosity & channels of (~5–10 Å) Al2(SO4)3 TMB-TTMT Hydro(solvo)thermal 3D framework with [38] in EtOH/water hexagonal channels (1.2 nm width) ZrCl4 BTBP Direct precipitation 3D amorphous and [39] & Hydrothermal semi-crystalline (HF) framework with microporosity (10 Å pores) ZrOCl2 TTBMP Direct precipitation 2D layered structure [40] in HF with no porosity Abbreviations: DPA = Diphosphonic acid; N,N’-PBMDPA = N,N’-piperazine bis(methylenephosphonic acid); DHBP = 1,4-dihydroxy-2,5-benzenediphosphonate; EDTP = N,N,N’,N’- ethylenediaminetetrakis(methylenephosphonic acid); PBMPA = Piperazine-N,N’-bis(methylenephosphonic acid); BDPEt = 1,4-benzenediphosphonate bis(monoethyl ester); BDPMe = 1,4-benzenediphosphonate bis(monomethyl ester); BDPA = Benzene-1,4-diphosphonic acid; BTTMT = Benzene-1,3,5- triyltris(methylene)triphosphonic acid; TMB-BTTMT = (2,4,6-trimethylbenzene-1,3,5- triyl)tris(methylene)triphosphonic acid; BTBP = 1,3,5-tris(4-phosphonophenyl) benzene; TTBMP = 2,4,6-tris(4- (phosphonomethyl)phenyl)-1,3,5-triazine; and TMB-TTMT = 2,4,6-trimethylbenzene-1,3,5-triyl- tris(methylene)triphosphonic acid. Table S3. Mesoporous Metal Phosphonates—Templated. Metal Phosphonic Template Synthesis Method Final Morphology References Precursor Acid Amorphous, Co-condensation at Al(OiPr)3 MDPA ODTMACl Mesoporous (1.8 [41] RT in water nm pores) Amorphous, Atrane route, Co- Al(OsBu)3 EDPA CTAB Mesoporous [42] precipitation in water (hexagonal) Brij-56/58 Co-condensation in Amorphous AlCl3 MDPA F68, F127 EtOH/water followed [43] Mesoporous (p6m) P123 by EISA MDPA Co-condensation in Al(OiPr)3 Amorphous with EDPA CTAB water and [44] AlCl3 Mesoporosity PDPA EtOH/water Semi-crystalline, SnCl4 PPA SDS Hydrothermal Micro and [45] mesoporous Amorphous, Inter- Hydrothermal in ZrOCl2 PPA - particle [46] water mesoporosity Atrane route, Co- Amorphous with Al(OsBu)3 H3PMP CTAB [47] precipitation in water mesoporosity Amorphous with Non-hydrolytic Ti(OiPr)4 TPPhA - inter-particle [48] condensation in THF porosity Non-hydrolytic Amorphous with V(O)(OiPr)3 TPPhA - condensation in inter-particle [49] DMSO porosity Materials 2020, 13, 5366 4 of 7 Amorphous, Inter- HEDP Hydrothermal in particle Ti(OBu)4 PS beads [50] (β-CD) EtOH/water mesoporosity & macroporous Amorphous, plate- like particles & slit HEDP Hydrothermal in Ti(OBu)4 - shaped inter- [51] EDTMP EtOH/water particle mesoporosity Co-condensation in Amorphous, Inter- F127 Ti(OBu)4 HEDP EtOH followed by particle [52] P123 EISA mesoporosity Cryogenic condensation in EtOH Amorphous, p6mm TiCl4 EDTMP Brij-56 [53] followed by Mesophase hydrothermal and EISA Cryogenic condensation in Amorphous, la3d TiCl4 HEDP CTAB EtOH followed by [54] cubic mesophase hydrothermal treatment Amorphous with HEDP Hydrothermal in hierarchical Ti(OBu)4 - [55] EDTMP EtOH/water meso/macroporosit y Crystalline (anatase domains) with EDTMP Hydrothermal in phosphonate cap Ti(OBu)4 - [56] DTPMP EtOH/water and hierarchical meso/macroporosit y Amorphous, Cubic Co-condensation in AlCl3 BDPA F127 mesoporous [57] EtOH/water (Im3m) DEPT Amorphous, Co-condensation in AlCl3 DPAEP F127 mesoporous thin [58] EtOH/water DPEP film Anatase Non-hydrolytic sol crosslinked bBzP Ti(OiPr)4 - gel hydrothermal in bisphosphonates [59] bPyP toluene with inter-crystal mesopores Abbreviations: MDPA = Methylenediphosphonic acid; EDPA = Ethylenediphosphonic acid; PDPA = Propylenediphosphonic acid; PPA = Phenylposphonic acid; H3PMP = 1-phosphonomethylproline; TPPhA = Tetrakis-1,3,5,7-(4-diethylphosphonatophenyl) adamantane; HEDP = 1-hydroxyethane 1,1-diphosphonic acid; EDTMP = Ethylenediamine tetra(methylene phosphonic acid); DTPMP = Diethylenetriamine penta(methylene phosphonic acid); BDPA = 1,4-phenylene diphosphonic acid; DEPT = 2,5-bis(diethoxyphosphoryl) thiophene; DPAEP = Diethyl (N-diethylphosphonomethylcarbonyl)aminoethyl phosphonate; DPEP = Diethyl 2-(2’- diethylphosphonoethoxy)ethylphosphonate; bBzP = 4,4’-bis(diethylphosphonomethyl)biphenyl; and bByP = tetraethyl 2,2’-bipyridine-5,5’-bisphosphonate. Materials 2020, 13, 5366 5 of 7 References 1. Dines, M.B.; Digiacomo, P.M. Derivatized lamellar phosphates and phosphonates of M (IV) ions. Inorg. Chem. 1981, 20, 92–97, doi:10.1021/ic50215a022. 2. Dines, M.B.; Griffith, P.C. Synthesis and characterization of layered tetravalent metal terphenyl mono- and bis-phosphonates. Polyhedron 1983, 2, 607–611, doi:10.1016/s0277-5387(00)81519-3. 3. Cao, G.; Hong, H.G.; Mallouk, T.E. Layered metal phosphates and phosphonates: from crystals to monolayers. Accounts Chem. Res. 1992, 25, 420–427, doi:10.1021/ar00021a007. 4. Alberti, G.;