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Title: Synthesis and characterization of four new metal 5-phosphonoisophthalates discovered by high-throughput experimentation

Abstract

A new ligand, 5-diethylphosphonoisophthalic acid ((HOOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}(C{sub 2}H{sub 5}){sub 2}, H{sub 2}Et{sub 2}L), for the hydrothermal synthesis of inorganic-organic hybrid compounds was prepared and characterized by NMR-spectroscopy. Its in situ hydrolysis leads to the corresponding 5-phosphonoisophthalic acid ((HOOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}H{sub 2}, H{sub 4}L). Applying high-throughput methods, different di- and trivalent metal salts for the synthesis of crystalline metal phosphonates based on H{sub 2}Et{sub 2}L have been screened. From the resulting discovery library, single-crystals of four new compounds, [Sm{sub 2}(H{sub 2}O){sub 4}(H(OOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}){sub 2}].2H{sub 2}O (1), [Cu{sub 3}(H{sub 2}O)(H(OOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}){sub 2}].2H{sub 2}O (2), Ca{sub 2}(H{sub 2}O)[H(OOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}H]{sub 2} (3), and Ba{sub 2}(H{sub 2}O){sub 3}(OOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3} (4), have been isolated. The single-crystal structure determination of the title compounds shows H{sub 4}L to be a versatile ligand, exhibiting different types of coordination modes between the functional groups and the metal ions. A comparison of the structural features of the title compounds shows a varying degree of M-O-M connectivities. Thus, isolated metal-oxygen clusters (compounds 1 and 2), infinite M-O-M chains (compound 3), and infinite M-O-M layers (compound 4) are observed. The title compounds 1, 2, and 3more » were further characterized by IR-spectroscopy, TG-, EDX-, and elemental chemical analysis. - Graphical abstract: Applying high-throughput methods, the new ligand 5-diethylphosphonoisophtalic acid, (HOOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}(C{sub 2}H{sub 5}){sub 2} (H{sub 2}Et{sub 2}L), was reacted with several di- and trivalent metal salts under hydrothermal conditions. Single-crystals of four new inorganic-organic hybrid compounds were isolated from the discovery library. The single-crystal structure analysis shows a varying M-O-M connectivity.« less

Authors:
 [1];  [2]
  1. Institute of Inorganic Chemistry, Christian-Albrechts-University, Otto-Hahn-Platz 6/7, D 24098 Kiel (Germany)
  2. Institute of Inorganic Chemistry, Christian-Albrechts-University, Otto-Hahn-Platz 6/7, D 24098 Kiel (Germany), E-mail: stock@ac.uni-kiel.de
Publication Date:
OSTI Identifier:
21043733
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 11; Other Information: DOI: 10.1016/j.jssc.2007.08.026; PII: S0022-4596(07)00370-2; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BARIUM COMPLEXES; CALCIUM COMPLEXES; CHEMICAL ANALYSIS; COPPER COMPLEXES; CRYSTAL STRUCTURE; HYDROLYSIS; HYDROTHERMAL SYNTHESIS; INFRARED SPECTRA; LAYERS; LIGANDS; MONOCRYSTALS; PHOSPHONATES; PHTHALATES; SAMARIUM COMPLEXES; SPECTROSCOPY; WATER

Citation Formats

Bauer, Sebastian, and Stock, Norbert. Synthesis and characterization of four new metal 5-phosphonoisophthalates discovered by high-throughput experimentation. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2007.08.026.
Bauer, Sebastian, & Stock, Norbert. Synthesis and characterization of four new metal 5-phosphonoisophthalates discovered by high-throughput experimentation. United States. doi:10.1016/j.jssc.2007.08.026.
Bauer, Sebastian, and Stock, Norbert. Thu . "Synthesis and characterization of four new metal 5-phosphonoisophthalates discovered by high-throughput experimentation". United States. doi:10.1016/j.jssc.2007.08.026.
@article{osti_21043733,
title = {Synthesis and characterization of four new metal 5-phosphonoisophthalates discovered by high-throughput experimentation},
author = {Bauer, Sebastian and Stock, Norbert},
abstractNote = {A new ligand, 5-diethylphosphonoisophthalic acid ((HOOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}(C{sub 2}H{sub 5}){sub 2}, H{sub 2}Et{sub 2}L), for the hydrothermal synthesis of inorganic-organic hybrid compounds was prepared and characterized by NMR-spectroscopy. Its in situ hydrolysis leads to the corresponding 5-phosphonoisophthalic acid ((HOOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}H{sub 2}, H{sub 4}L). Applying high-throughput methods, different di- and trivalent metal salts for the synthesis of crystalline metal phosphonates based on H{sub 2}Et{sub 2}L have been screened. From the resulting discovery library, single-crystals of four new compounds, [Sm{sub 2}(H{sub 2}O){sub 4}(H(OOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}){sub 2}].2H{sub 2}O (1), [Cu{sub 3}(H{sub 2}O)(H(OOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}){sub 2}].2H{sub 2}O (2), Ca{sub 2}(H{sub 2}O)[H(OOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}H]{sub 2} (3), and Ba{sub 2}(H{sub 2}O){sub 3}(OOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3} (4), have been isolated. The single-crystal structure determination of the title compounds shows H{sub 4}L to be a versatile ligand, exhibiting different types of coordination modes between the functional groups and the metal ions. A comparison of the structural features of the title compounds shows a varying degree of M-O-M connectivities. Thus, isolated metal-oxygen clusters (compounds 1 and 2), infinite M-O-M chains (compound 3), and infinite M-O-M layers (compound 4) are observed. The title compounds 1, 2, and 3 were further characterized by IR-spectroscopy, TG-, EDX-, and elemental chemical analysis. - Graphical abstract: Applying high-throughput methods, the new ligand 5-diethylphosphonoisophtalic acid, (HOOC){sub 2}C{sub 6}H{sub 3}-PO{sub 3}(C{sub 2}H{sub 5}){sub 2} (H{sub 2}Et{sub 2}L), was reacted with several di- and trivalent metal salts under hydrothermal conditions. Single-crystals of four new inorganic-organic hybrid compounds were isolated from the discovery library. The single-crystal structure analysis shows a varying M-O-M connectivity.},
doi = {10.1016/j.jssc.2007.08.026},
journal = {Journal of Solid State Chemistry},
number = 11,
volume = 180,
place = {United States},
year = {Thu Nov 15 00:00:00 EST 2007},
month = {Thu Nov 15 00:00:00 EST 2007}
}
  • The PbFe{sub 3}O(PO{sub 4}){sub 3} powder compound was studied by means of X-ray diffraction (XRD) from 300 to 6 K, electron-probe microanalysis (EPMA) coupled with wavelength dispersion spectroscopy (WDS), calorimetric (DSC and specific heat) and magnetic properties measurements. Magnetization, magnetic susceptibility and specific heat measurements carried out on PbFe{sub 3}O(PO{sub 4}){sub 3} powders firmly establish a series of three ferromagnetic (FM)-like second order phase transitions spanned over the 32–8 K temperature range. Discrepancies between magnetization and specific heat data obtained in PbFe{sub 3}O(PO{sub 4}){sub 3} powders and single crystals are highlighted. A first extraction of the critical exponents (β,γ,δ) wasmore » performed by ac magnetic susceptibility in both PbFe{sub 3}O(PO{sub 4}){sub 3} powders and single crystals and the values were found to be consistent with mean-field theory. Further exploration of the PbO–Fe{sub 2}O{sub 3}–P{sub 2}O{sub 5} system led to the discovery of a new langbeinite phase, Pb{sub 1.5}Fe{sub 2}(PO{sub 4}){sub 3}, the crystal structure of which was solved by room temperature single crystal XRD (P2{sub 1}3, Z=4, a=9.7831(2) Å). This phase does not undergo any structural phase transition down to 6 K nor any kind of long range ordering down to 2 K. - Graphical abstract: Three ferromagnetic-like phase transitions discovered in the new compound PbFe{sub 3}O(PO{sub 4}){sub 3} by specific heat and ZFC/FC magnetization measurements. - Highlights: • Three FM-like second order phase transitions in PbFe{sub 3}O(PO{sub 4}){sub 3} powders. • Critical exponents (β,γ,δ) in PbFe{sub 3}O(PO{sub 4}){sub 3} consistent with mean-field behavior. • Discovery of a new langbeinite phase, Pb{sub 1.5}Fe{sub 2}(PO{sub 4}){sub 3}.« less
  • Design and operation of a “six-flow fixed-bed microreactor” setup for Fischer-Tropsch synthesis (FTS) is described. The unit consists of feed and mixing, flow division, reaction, separation, and analysis sections. The reactor system is made of five heating blocks with individual temperature controllers, assuring an identical isothermal zone of at least 10 cm along six fixed-bed microreactor inserts (4 mm inner diameter). Such a lab-scale setup allows running six experiments in parallel, under equal feed composition, reaction temperature, and conditions of separation and analysis equipment. It permits separate collection of wax and liquid samples (from each flow line), allowing operation with highmore » productivities of C5+ hydrocarbons. The latter is crucial for a complete understanding of FTS product compositions and will represent an advantage over high-throughput setups with more than ten flows where such instrumental considerations lead to elevated equipment volume, cost, and operation complexity. The identical performance (of the six flows) under similar reaction conditions was assured by testing a same catalyst batch, loaded in all microreactors.« less
  • Using high-throughput instrumentation to screen conditions, the reaction between FeCl₂ and H₃BTT∙2HCl (BTT 3- = 1,3,5-benzenetristetrazolate) in a mixture of DMF and DMSO was found to afford Fe₃[(Fe₄Cl)₃(BTT)₈]₂∙22DMF∙32DMSO∙11H₂O. This compound adopts a porous three-dimensional framework structure consisting of square [Fe₄Cl] 7+ units linked via triangular BTT 3- bridging ligands to give an anionic 3,8-net. Mössbauer spectroscopy carried out on a DMF-solvated version of the material indicated the framework to contain high-spin Fe 2+ with a distribution of local environments and confirmed the presence of extra-framework iron cations. Upon soaking the compound in methanol and heating at 135 °C for 24more » h under dynamic vacuum, most of the solvent is removed to yield Fe₃[(Fe₄Cl)₃(BTT)₈(MeOH)₄]₂ (Fe-BTT), a microporous solid with a BET surface area of 2010 m 2 g -1 and open Fe 2+ coordination sites. Hydrogen adsorption data collected at 77 K show a steep rise in the isotherm, associated with an initial isosteric heat of adsorption of 11.9 kJ mol -1, leading to a total storage capacity of 1.1 wt% and 8.4 g L -1 at 100 bar and 298 K. Powder neutron diffraction experiments performed at 4 K under various D₂ loadings enabled identification of ten different adsorption sites, with the strongest binding site residing just 2.17(5) Å from the framework Fe 2+ cation. Inelastic neutron scattering spectra are consistent with the strong rotational hindering of the H₂ molecules at low loadings, and further reveal the catalytic conversion of ortho-H₂ to para-H₂ by the paramagnetic iron centers. The exposed Fe 2+ cation sites within Fe-BTT also lead to the selective adsorption of CO₂ over N₂, with isotherms collected at 298 K indicating uptake ratios of 30.7 and 10.8 by weight at 0.1 and 1.0 bar, respectively.« less
  • The reactions of aryl-, alkyl-, and alkoxy-substituted phosphorus hydrazides, RP(E)(NMeNH[sub 2])[sub 2] (R = Ph, E = S, I; R = OEt, E = S, 2; R = Ph, E = O, 3; R = Et, E = O, 4; R = Me, E = O, 5) with ferrocenecarboxaldehyde gave metallocene-functionalized phosphorus hydrazides in good yields (approximately 90-95%) as air-stable crystalline solids with the following chemical compositions: RP(E)(NMeNCHCp[prime]FeCp)[sub 2] (R = Ph, E = S, 6; R = OEt, E = S, 7; R = Ph, E = O, 8; R = Et, E = O, 9; R = Me,more » E = O, 10). These ferrocenyl phosphorus hydrazides 6-10 can be used as versatile synthons to produce new heterometallic organometallic compounds. The chemical constitutions of 6-10 and 11-15 were established by complete NMR ([sup 1]H and [sup 31]P) spectroscopic and C, H, and N analysis. As representative examples, X-ray structures of 7 and 12 have been determined. Crystal data for C[sub 2]H[sub 5]OP(S)(NMeNCHCp[prime]FeCp)[sub 2], 7: orthorhombic, space group P2[sub 1]2[sub 1]2[sub 1], a = 7.5556(11) [angstrom], b = 10.7652(12) [angstrom], c = 33.186(4) [angstrom], V = 2699.3(3) [angstrom][sup 3], Z = 4. The structure was solved by direct methods and was refined to R = 0.038. The structure of 12 comprises the neutral monomeric trimetallic complex C[sub 2]H[sub 5]OP(S)(NMeNCHCp[prime]FeCp)[sub 2][center dot]PdCl[sub 2] with the Pd(II) center in a square planar geometry. The structure of 12 is characterized by a six-membered ring with the Pd(II) bonded to two terminal hydrazine units of 7 in a cis disposition. Crystal data of 12: monoclinic, space group P2[sub 1]/c, a = 15.731(3) [angstrom], l = 18.695(3) [angstrom], c = 11.918(2) [angstrom], [beta] = 98.180(7)[degree], V = 3469.3(10) [angstrom][sup 3], Z = 4. The structure was solved by direct methods and was refined to R = 0.033. 21 refs., 2 figs., 6 tabs.« less