Hydrogen Phosphonate Research Articles

Mediating Order and Modulating Porosity by Controlled Hydrolysis in a Phosphonate Monoester Metal–Organic Framework

AbstractA crystalline and permanently porous copper phosphonate monoester framework has been synthesized from a tetraaryl trigonal phosphonate monoester linker. This material has a surface area over 1000 m2 g−1, as measured by N2 sorption, the highest reported for a phosphonate‐based metal–organic framework (MOF). The monoesters result in hydrophobic pore surfaces that give a low heat of adsorption for CO2 and low calculated selectivity for CO2 over N2 and CH4 in binary mixtures. By careful manipulation of synthetic conditions, it is possible to selectively remove some of the monoesters lining the pore to form a hydrogen phosphonate while giving an isomorphous structure. This increases the affinity of the framework for CO2 giving higher ambient uptake, higher heat of adsorption, and much higher calculated selectivity for CO2 over both N2 and CH4. Formation of the acid groups is noteworthy as complexation with the parent acid gives a different structure.

Hydrogen bonding, π-π stacking and van der Waals forces-dominated layered regions in the crystal structure of 4-amino-pyridinium hydrogen (9-phosphono-non-yl)phospho-nate.

The asymmetric unit of the title mol-ecular salt, [C5H7N2+][(HO)2OP(CH2)9PO2(OH)-], consists of one 4-amino-pyridinium cation and one hydrogen (9-phos-phono-non-yl)phospho-nate anion, both in general positions. As expected, the 4-amino-pyridinium moieties are protonated exclusively at their endocyclic nitro-gen atom due to a mesomeric stabilization by the imine form which would not be given in the corresponding double-protonated dicationic species. In the crystal, the phosphonyl (-PO3H2) and hydrogen phospho-nate (-PO3H) groups of the anions form two-dimensional O-H⋯O hydrogen-bonded networks in the ab plane built from 24-membered hydrogen-bonded ring motifs with the graph-set descriptor R66(24). These networks are pairwise linked by the anions' alkyl-ene chains. The 4-amino-pyridinium cations are stacked in parallel displaced face-to-face arrangements and connect neighboring anionic substructures via medium-strong charge-supported N-H⋯O hydrogen bonds along the c axis. The resulting three-dimensional hydrogen-bonded network shows clearly separated hydro-philic and hydro-phobic structural domains.

Organo-phosphorus flame retardants for unsaturated polyester derived from recycled poly(ethylene terephthalate)

In an attempt to suppress the flammability of unsaturated polyesters (RUP) derived from recycled poly(ethylene terephthalate) (PET) and investigate the relationship between flame retardant (FR) chemical structures and their flame retardancy, RUP was incorporated with four organo-phosphorus FRs; triphenyl phosphate (TPP), aluminum hydrogen phosphonate (AHP), diammonium hydrogen phosphate (DAP), and aluminum diethyl phosphinate (OP). The effects of adding FR with regard to the thermal stability of RUP/FR mixtures were investigated via thermogravimetric analysis (TGA). The chemical structure of FR and its mixtures with RUP were determined via FTIR and X-ray photoelectron spectroscopy (XPS). The morphology of the residual char was investigated using a field emission scanning electron microscope (FE-SEM). Flame retardancies were evaluated by a UL-94 vertical test and limiting oxygen index (LOI) measurements. The results indicated that the presence of FR significantly improved the flame retardancy and thermal stability of RUP. LOI values increased from 20 to 28 and V-0 ratings were obtained with an 8 wt% FR loading for DAP and with a 10 wt% FR loading for OP. In contrast, no ratings were recorded for the mixture containing 30 wt% of TPP or AHP. These findings clearly indicate that the efficiency of a phosphorus-based FR depends on the quantity of phosphorus elements within the FR itself, although interactions of the FR with the target polymer should also be accounted for when determining its effectiveness as a FR.

Organo‐Phosphorus Flame Retardants for Poly(vinyl chloride)/Wood Flour Composite

A series of organo‐phosphorus flame retardants (FRs) were studied in order to investigate their flame retarding performances for poly(vinyl chloride)/wood flour (PVC‐WF) composite. The FRs used include diammonium hydrogen phosphate (DAP), aluminum hydrogen phosphonate (AHP), and triphenyl phosphate (TPP). The effects of incorporating different FRs into PVC‐WF were determined by UL‐94, TGA, FTIR, and field emission scanning electron microscope (FE‐SEM). The results revealed significantly improved flame retardancy and thermal stability of PVC‐WF in the presence of FR. V‐0 ratings can be obtained at loading of FR as low as 1 wt% for DAP and 1.5 wt% for TPP but the same rating is recorded for the mixture containing 20 wt% AHP. AHP mainly acted in condensed phase whereas TPP and DAP generated phosphorus volatiles and/or fuel dilution compounds. TGA analysis was utilized to calculate the kinetic parameters of PVC‐WF and PCV‐WF/FR as well as to study the interaction between FR and PVC‐WF. FE‐SEM and FTIR were used to examine the morphologies and chemical components of the residual char. The results showed that PVC‐WF/FR produced phosphorus‐containing moieties during decomposition, which could act as dehydration agents to form char layer to protect the mixture from further degradation. The flexural and impact properties of composite increased with addition of FR at low loading and decreased with high loading of FR. By the incorporation of TPP in PVC‐WF, the glass transition is decreased; however, the storage modulus in the low‐temperature glass state is increased. This effect is attributed to antiplasticizing ability of TPP for PVC‐WF system. POLYM. COMPOS., 39:961–970, 2018. © 2016 Society of Plastics Engineers

A Water Stable Magnesium MOF That Conducts Protons over 10(-2) S cm(-1).

From the outset of the study of MOFs as proton conductors, both conductivity and hydrolytic robustness of the materials have needed to be improved. Here, we report a layered magnesium carboxyphosphonate framework, PCMOF10, that shows an extremely high proton conductivity value of 3.55 × 10(-2) S·cm(-1) at 70 °C and 95% RH. Moreover, PCMOF10 is water stable owing to strong Mg phosphonate bonding. The 2,5-dicarboxy-1,4-benzenediphosphonic acid (H6L) linker anchors a robust backbone and has hydrogen phosphonate groups that interact with the lattice water to form an efficient proton transfer pathway.

Supercritical fluid extraction of uranium and thorium from nitric acid medium using organophosphorous compounds

Abstract In recent years, Supercritical Fluid Extraction (SFE) technique has been widely used for the extraction of metal ions. In the present study, extraction of uranium from nitric acid medium was investigated using supercritical carbon dioxide (Sc-CO2) containing various organophosphorous compounds such as trialkyl phosphates e.g. tri-iso-amyl phosphate (TiAP), tri-sec-butyl phosphate (TsBP) and tri-n-butyl phosphate (TBP), dialkylalkyl phosphonates, e.g. diamylamyl phosphonate (DAAP) and dibutyl butyl phosphonate (DBBP), dialkyl hydrogen phosphonates, e.g. dioctyl hydrogen phosphonate (DOHP), dioctylphosphineoxide (DOPO), trioctyl phosphine oxide (TOPO), n-octylphenyl N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO) and di-2-ethyl-hexyl phosphoric acid (HDEHP). Some of these ligands have been investigated for the first time in the supercritical phase for the extraction of uranium. The extraction efficiency of uranium was studied with TiAP, DAAP and DBBP as a function of nitric acid concentration; the kinetics of the equilibration period (static extraction) and transportation of the metal complex (dynamic extraction) was investigated. The influence of pressure and temperature on the extraction behaviour of uranium with DAAP was studied from 4 N HNO3. The extraction efficiency of uranium from 4 N nitric acid medium was found to increase in the order of phosphates < phosphonates < HDEHP < TOPO < CMPO. In the case of phosphates and phosphonates, the maximum extraction of uranium was found to be from 4 N HNO3 medium. The acidic extractants, HDEHP and DOHP showed relatively higher extraction at lower acidities. The relative extraction of uranium and thorium from their mixture was also examined using Sc-CO2 containing phosphates, phosphonates and TOPO. The ligand, TsBP provided better fractionation between uranium and thorium compared to trialkyl phosphates, dialkyl alkyl phosphonates and TOPO.

Synthesis and structural studies of diorganotin(IV)-based coordination polymers bearing silaalkylphosphonate ligands and their transformation into colloidal domains.

The contribution of silaalkylphosphonic acids Me3SiCH2P(O)(OH)2 (1) and Me3SiC(CH3)2P(O)(OH)2 (2) as ligands was demonstrated for the first time by the isolation of new diorganotin(IV) phosphonates Et2Sn{OP(O)(OH)CH2SiMe3}(OSO2Me) (3), (Et2Sn)6{O3PC(CH3)2SiMe3}4(OSO2Me)4 (4), and Et2Sn(O3PCH2SiMe3) (5). X-ray crystallographic studies of 1-4 are presented. The structures of 1 and 2 adopt extended motifs by virtue of P-OH···O═P-type hydrogen bonding interactions. The molecular structure of 3 is composed of a dimer formed by bridging hydrogen phosphonate groups, while the sulfonate group appended on each tin atom acts in a μ2-bridging mode to afford the formation of one-dimensional coordination polymer featuring alternate eight-membered [-Sn-O-P-O-]2 and [-Sn-O-S-O-]2 rings. The asymmetric unit of 4 is composed of two crystallographically unique trinuclear tin phosphonate clusters with a Sn3(μ3-PO3)2 core linked together by coordinative association of a μ2-sulfonate group, while the remaining sulfonates are involved in the construction of a two-dimensional self-assembly. The identity of 1-5 in solution was established by IR and multinuclear ((1)H, (13)C, (31)P, (119)Sn) NMR spectroscopy. The presence of silaalkyl group in 5 imparts unusual solubility in hydrocarbon, aromatic, and ether solvents. As a consequence, the formation of colloidal particles of 5 featuring rodlike morphology was achieved by ultrasonication of a solution in ethanol-chloroform mixture.

Poly[[μ-(1-azaniumylethane-1,1-diyl)bis(hydrogen phosphonato)]sodium]: a powder X-ray diffraction study

The title two-dimensional coordination polymer, [Na(C₂H₈NO₆P₂)]n, was characterized using powder X-ray diffraction data and its structure refined using the Rietveld method. The asymmetric unit contains one Na⁺ cation and one (1-azaniumylethane-1,1-diyl)bis(hydrogen phosphonate) anion. The central Na⁺ cation exhibits distorted octahedral coordination geometry involving two deprotonated O atoms, two hydroxy O atoms and two double-bonded O atoms of the bisphosphonate anion. Pairs of sodium-centred octahedra share edges and the pairs are in turn connected to each other by the biphosphonate anion to form a two-dimensional network parallel to the (001) plane. The polymeric layers are connected by strong O-H∙∙∙O hydrogen bonding between the hydroxy group and one of the free O atoms of the bisphosphonate anion to generate a three-dimensional network. Further stabilization of the crystal structure is achived by N-H∙∙∙O and O-H∙∙∙O hydrogen bonding.

Enhancing Proton Conduction in a Metal–Organic Framework by Isomorphous Ligand Replacement

Using the concept of isomorphous replacement applied to entire ligands, a C(3)-symmetric trisulfonate ligand was substituted with a C(3)-symmetric tris(hydrogen phosphonate) ligand in a proton conducting metal-organic framework (MOF). The resulting material, PCMOF2½, has its proton conduction raised 1.5 orders of magnitude compared to the parent material, to 2.1 × 10(-2) S cm(-1) at 90% relative humidity and 85 °C, while maintaining the parent MOF structure.

The supramolecular architecture of tris(naphthalene-1,5-diaminium) bis(5-aminonaphthalen-1-aminium) octakis[hydrogen (5-carboxypyridin-3-yl)phosphonate

The asymmetric unit of the title compound, 3C(10)H(12)N(2)(2+)·2C(10)H(11)N(2)(+)·8C(6)H(5)NO(5)P(-), contains one and a half naphthalene-1,5-diaminium cations, in which the half-molecule has inversion symmetry, one 5-aminonaphthalen-1-aminium cation and four hydrogen (5-carboxypyridin-3-yl)phosphonate anions. The crystal structure is layered and consists of hydrogen-bonded anionic monolayers between which the cations are arranged. The acid monoanions are organized into one-dimensional chains along the [101] direction via hydrogen bonds established between the phosphonate sites. (C)O-H···N(py) hydrogen bonds (py is pyridine) crosslink the chains to form an undulating (010) monolayer. The cations serve both to balance the charge of the anionic network and to connect neighbouring layers via multiple hydrogen bonds to form a three-dimensional supramolecular architecture.

Abundant Intramolecular Ring Rearrangements of 1-(N-Benzyloxycarbonylamino)arylmethylphosphonate Phenyl monoesters Under Electrospray Ionization Conditions

The mass spectrometric behavior of 1-(N-benzyloxycarbonylamino)arylmethyl-phosphonate phenyl monoesters was investigated under positive ion electrospray ionization conditions. All nitrogen-protonated title compounds undergo four- and/or six-membered ring rearrangements to yield nitrogen-containing fragment ions by consecutive or simultaneous loss of a carbon dioxide and phenyl hydrogen phosphonate or phenyl benzylphosphonate or an arylmethylimine. All oxygen-protonated title compounds undergo four- to six-membered ring rearrangements to produce fragment ions by loss of a carbon dioxide plus an arylmethylimine, or phenyl benzylphosphonate, by consecutive or simultaneous loss of benzyl phenyl ether and isocyanic acid. The fragmentation is obviously different from the corresponding methyl and ethyl monoesters, which show a tendency to undergo intramolecular four-membered ring rearrangements only.GRAPHICAL ABSTRACT

Potent inhibition of protein tyrosine phosphatases by quinquedentate binuclear copper complexes: synthesis, characterization and biological activities

Three phosphono-containing multidentate ligands were employed to synthesize quinquedentate binuclear copper complexes, [Cu(2)L(2)] (1-3) (H(2)L1 = diethyl(propane-1,3-diylbis(azanediyl))bis((2-hydroxyphenyl)methylene)bis(hydrogen phosphonate), H(2)L2 = diethyl(ethane-1,2-diylbis(azanediyl))bis((2-hydroxyphenyl)methylene)bis(hydrogen phosphonate), H(2)L3 = diethyl(hexane-1,6-diylbis(azanediyl))bis((2-hydroxyphenyl)methylene)bis(hydrogen phosphonate)), which were characterized by elemental analysis, IR, X-ray diffraction analysis, electrospray ionization mass spectra. Complexes 1 and 2 crystallized in the triclinic system with space group P ̅1. The speciation of the Cu-H(2)L1 system in aqueous solution was investigated by potentiometric pH titrations. The three dicopper complexes exhibited potent and almost the same inhibitory effects against protein tyrosine phosphatase 1B (PTP1B) and T-cell protein tyrosine phosphatase (TCPTP) with IC(50) of 0.16-0.24 μM, about 10-fold stronger inhibition than against Src homology phosphatase 1 (SHP-1), 30-fold than against Src homology phosphatase 2 (SHP-2) and more than 100-fold than against megakaryocyte protein-tyrosine phosphatase 2 (PTP-MEG2). Fluorescence titrations revealed complex 1 bond to the five PTPs with molar ratio of 1:1 and binding constants of 1.62 × 10(6), 3.09 × 10(6), 1.95 × 10(5), 2.24 × 10(5), 1.55 × 10(4) M(-1) for PTP1B, TCPTP, SHP-1, SHP-2 and PTP-MEG2, respectively, consistent with the inhibitory abilities from IC(50) and K(i) values. Also, the three copper complexes could inhibit phosphatase activity of cell extracts from C6 rat glioma cells. The results suggested the structures of copper complexes influence selectivity over different PTPs.

P–H activation using alkynylgold substrates: steric and electronic effects

The susceptibility of a prototypical hydrogen phosphonate to undergo P-H activation upon treatment with alkynylgold complexes has been studied. Dynamic solution behavior was observed during reactions involving triphenylphosphine ligated substrates and was attributed to rapid phosphine exchange between the alkynylgold starting material and the gold phosphonate product. The use of bulky biaryldialkylphosphine ligands eliminated the fluxional behavior, but did not significantly slow the rate of P-H activation. Similarly, changing the supporting ligand to an N-heterocyclic carbene did not significantly slow the rate of the reaction. Despite a number of reports outlining the functionalization of propargyl alcohols using gold catalysts, incorporating these groups into the architecture of the alkynylgold substrates did not alter the product distributions. Although the chemistry tolerated a range of supporting ligands, incorporating electron donating groups into the alkyne increased the rate of the reaction while electron-withdrawing groups slowed the reaction. A possible mechanism for the process includes a transition state containing significant pi-contribution from the alkyne. Due to the high yields of gold phosphonates obtained in this chemistry as well as the mild conditions of the reactions, the interception of intermediates/catalysts by substrates or ligands containing labile P-H donors is an issue that must be circumvented when designing or developing a gold catalyzed reaction that proceeds through alkynylgold intermediates.

ChemInform Abstract: Study of the Reactions of Dimethyl Hydrogen Phosphonate with Urethane and Acetanilide.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Ring opening insertion polymerization of ε‐caprolactone with hydrogen phosphonate initiators

AbstractIn this work, ring opening insertion polymerization (ROIP) of ε‐caprolactone (ε‐CL) using a series of hydrogen phosphonates (H‐phosphonates) as initiators was investigated. The ROIP occurred by a coordination‐insertion mechanism containing two steps. First, the carbonyl carbon was attacked by the phosphorus atom of the H‐phosphonate tautomerization (a phosphine‐like structure) and the acyl‐oxygen bond was broken. An intermediate was formed by the coordination of the former carbonyl carbon and acyl‐oxygen of ε‐CL to phosphorus atom. Then the phosphorus‐alkoxide of H‐phosphonate was cleavaged to form acyl‐alkoxide bond. Poly(ε‐caprolactone) (PCL)‐inserted H‐phosphonates (PCL‐HPs), which was not only the product of the occurred ROIP but also the initiator for the next ROIP, were produced. After 60 min of microwave irradiation (510 W), PCL with a number‐average molar mass of 7800 g/mol and monomer conversion over 92% was obtained. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6214–6222, 2009

Water-controlled reactions selectivity of the ReOCl 3(OPPh 3)(SMe 2) synthon with a hydrophosphorane ligand

The reaction of the hydrospirophosphorane HP(OCMe 2CMe 2O) 2 ligand or the five-membered cyclic hydrogen phosphonate HP(O)(OCMe 2CMe 2O) ligand with the ReOCl 3(OPPh 3)(SMe 2) precursor under controlled reaction conditions led to the isolation of dimeric oxo-rhenium(V) complexes containing P(O)(OCMe 2CMe 2O) − moieties, represented by [ReOCl 2{ μ-OP(OCMe 2CMe 2O)} 3ReOCl(OPPh 3)] ( 1) and [ReOCl 2(SMe 2){ μ-OP(OCMe 2CMe 2O)}] 2 ( 2). The chemical composition of these complexes was established by means of NMR, IR spectroscopic methods, and based on analytical data. The relative stereochemistry of 1 and 2 was unambiguously determined by single X-ray diffraction studies. The crystal structure of 1 comprises two crystallographically independent molecules in an asymmetric unit and co-crystallised molecules of both dichloromethane and acetonitrile. Two different six-coordinated monomeric subunits, ReOCl 2 and ReOCl(OPPh 3), connected by three phosphonate bridges, build up the dinuclear complex 1. It exhibits an uncommon feature, a cis disposition of the triphenylphosphine oxide molecule relative to the terminal Re O bond. The crystal structure of 2 includes four molecules, in which two equivalent rhenium subunits ReOCl 2(SMe 2) are linked by two P(O)(OCMe 2CMe 2O) − bridges.

Unexpected Course of Kabachnik-Fields Reaction in the Microwave Synthesis of Quinoline-Based α-Aminophosphonates

The course of Kabachnik-Fields reaction in the synthesis of 3-substituted quinoline-based α-aminophosphonates under microwave irradiation has been investigated. Some unexpected monoester hydrogen phosphonate derivatives, obtained along with diethyl phosphonates by reaction of quinoline-3-carboxaldehyde and aniline as well as 3- aminoquinoline and benzaldehyde, respectively, with diethyl phosphite, have been analyzed and discussed. Keywords: α-Aminophosphonate, quinoline, microwave-assisted reaction, Kabachnik-Fields reaction

Extraction of U(VI), Th(IV), Pu(IV), and Am(III) from nitric acid solutions with polyfunctional organophosphorus acids

Extraction of microamounts of U(VI), Th(IV), Pu(IV), and Am(III) nitrates from aqueous HNO3 solutions with solutions of (diphenylphosphinylmethyl)phenylphosphinic, (di-p-tolylphosphinylmethyl)phenylphosphinic, and (dioctylphosphinylmethyl)phosphinic acids and of butyl hydrogen (diphenylphosphinylmethyl)phosphonate in organic diluents was studied. The metal: extractant stoichiometric ratio in the extractable complexes was determined, and the diluent effect on the extraction efficiency was examined. The possibility of using a macroporous polymeric sorbent impregnated with (dioctylphosphinylmethyl)phenylphosphinic acid for concentrating metal ions from HNO3 solutions was demonstrated.

Highly Air-Stable Anionic Mononuclear and Neutral Binuclear Palladium(II) Complexes for C−C and C−N Bond-Forming Reactions

The short-bite aminobis(phosphonite), PhN{P(-OC10H6(mu-S)C10H6O-)}2 (2), containing a mesocyclic thioether backbone is synthesized by either treating PhN(PCl2)2 with 2 equiv of thiobis(2,2'-naphthol) or reacting chlorophosphite (-OC10H6(mu-S)C10H6O-)PCl (1) with aniline in the presence of a base. Treatment of 2 with an equimolar amount of Pd(COD)Cl2 in the presence of H2O affords a P-N-P-bridged and P,S-metalated binuclear complex, [PhN(P(-OC10H6(mu-S)C10H6O-)-kappaP)2Pd2Cl2{P(-OC10H6(mu-S)C10H6O-)(O)-kappaP,kappaS}2] (3), whereas the same reaction with 2 equiv of Pd(COD)Cl2 in the presence of H2O and Et3N produces the mononuclear anionic complex [{(-OC10H6(mu-S)C10H6O-)P(O)-kappaP,kappaS}PdCl2](Et3NH) (5). By contrast, reaction of 2 with 2 equiv of Pd(COD)Cl2 and H2O in the absence of Et3N gives the hydrogen phosphonate coordinated complex [{(-OC10H6(mu-S)C10H6O-)P(OH)}PdCl2] (4) which converts to the anionic complex in solution or in the presence of a base. Compound 2 on treatment with Pt(COD)X2 (X = Cl or I) afforded P-coordinated four-membered chelate complexes [PhN(P(-OC10H6(mu-S)C10H6O-)-kappaP)2PtX2] (6 X = Cl, 7 X = I). The crystal structures of compounds 2, 3, 5, and 7 are reported. Compound 3 is the first example of a crystallographically characterized binuclear palladium complex containing a bidentate bridging ligand and its hydrolyzed fragments forming metallacycles containing a palladium-phosphorus sigma bond. All palladium complexes proved to be very good catalysts for the Suzuki-Miyaura and Mizoroki-Heck cross-coupling and amination reactions with excellent turnover numbers (TON up to 1.46 x 105 in the case of the Suzuki-Miyaura reaction).

Diastereoselective formation of 18-membered ring BINOL-hydrogen phosphonate dimers - Quasi-covalent hydrogen bonds?

Diastereoselective syntheses of the unusual dimers, 4-heptyl-2-(2′-hydroxy-binaphthyl)hydrogen phosphonate (5) and the cyclohexyl analogue (7), are achieved by hydrolysis of 4-(3,5-dioxa-4-phosphacyclohepta[2,1-α;3,4-α′]-dinaphthalene-4-yloxy)heptane (4) and the cyclohexane analogue (6), respectively. Two out of eight possible pairs of monomers units are involved in the stereoselective formation of the dimer 5a of configuration BINOLR-PS:BINOLR-PS; this is determined by X-ray crystallographic data, which reveal a centrosymmetric, 18-membered ring structure with Ci symmetry, consisting of two monomers strongly hydrogen-bonded between the oxygen of P=O units and hydroxyl hydrogen atoms. Mass spectrometric, melting point, and thermal decomposition point data, as well as NMR data, support the presence of strong, quasi-covalent hydrogen bonds. Computational analysis suggests that the diastereoselectivity is controlled by molecularly constrained geometry of the monomer. Compound 7, although not characterized crystallographically, appears to be analogous to 5.Key words: 18-membered ring, phosphonate dimer, diastereoselectivity, hydrogen-bonds, computational analysis.