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Filippov, A., Soenen, H., Blom, J. & Antzutkin, O. N. (2023). Dynamics and Structure of a Bitumen Emulsion as Studied by 1H NMR Diffusometry. ACS Omega, 8(39), 36534-36542
Open this publication in new window or tab >>Dynamics and Structure of a Bitumen Emulsion as Studied by 1H NMR Diffusometry
2023 (English)In: ACS Omega, E-ISSN 2470-1343, Vol. 8, no 39, p. 36534-36542Article in journal (Refereed) Published
Abstract [en]

Self-diffusion in a bitumen emulsion was studied by H-1 NMR. The emulsion forms two phases: continuous and dispersed. The continuous aqueous phase contains mainly water, with the energy of activation of the diffusion process equal to that of bulk water, while its diffusivity is smaller than that of bulk water by a factor of 2. The dispersed phase consists of bitumen droplets containing confined water, whose dynamics is characterized by a fully restricted diffusion regime in cavities with sizes of similar to 0.11 mu m. Therefore, the studied bitumen emulsion can be described by a model of a complex multiple emulsion of the water/oil/water (WOW) type. The suggested model does agree well with data from H-1 NMR spectroscopy and diffusometry of the bitumen emulsion doped with paramagnetic MnSO4(aq) as well as with an additional H-1 NMR study of the emulsion structure, in which emulsion stability was compromised by freezing at 253 K.

Place, publisher, year, edition, pages
Amer Chemical Soc, 2023
National Category
Physical Chemistry Other Chemistry Topics
Research subject
Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-101967 (URN)10.1021/acsomega.3c05492 (DOI)001070217800001 ()2-s2.0-85174915693 (Scopus ID)
Funder
Swedish Research Council Formas, 2021-01515
Note

Validerad;2023;Nivå 2;2023-11-14 (marisr);

License fulltext: CC BY

Available from: 2023-10-31 Created: 2023-10-31 Last updated: 2023-11-14Bibliographically approved
Lin, C.-F., Karlsson, O., Das, O., Mensah, R. A., Mantanis, G. I., Jones, D., . . . Sandberg, D. (2023). High Leach-Resistant Fire-Retardant Modified Pine Wood (Pinus sylvestris L.) by In Situ Phosphorylation and Carbamylation. ACS Omega, 8(12), 11381-11396
Open this publication in new window or tab >>High Leach-Resistant Fire-Retardant Modified Pine Wood (Pinus sylvestris L.) by In Situ Phosphorylation and Carbamylation
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2023 (English)In: ACS Omega, E-ISSN 2470-1343, Vol. 8, no 12, p. 11381-11396Article in journal (Refereed) Published
Abstract [en]

The exterior application of fire-retardant (FR) timber necessitates it to have high durability because of the possibility to be exposed to rainfall. In this study, water-leaching resistance of FR wood has been imparted by grafting phosphate and carbamate groups of the water-soluble FR additives ammonium dihydrogen phosphate (ADP)/urea onto the hydroxyl groups of wood polymers via vacuum-pressure impregnation, followed by drying/heating in hot air. A darker and more reddish wood surface was observed after the modification. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, solid-state 13C cross-polarization magic-angle-spinning nuclear magnetic resonance (13C CP-MAS NMR), and direct-excitation 31P MAS NMR suggested the formation of C–O–P covalent bonds and urethane chemical bridges. Scanning electron microscopy/energy-dispersive X-ray spectrometry suggested the diffusion of ADP/urea into the cell wall. The gas evolution analyzed by thermogravimetric analysis coupled with quadrupole mass spectrometry revealed a potential grafting reaction mechanism starting with the thermal decomposition of urea. Thermal behavior showed that the FR-modified wood lowered the main decomposition temperature and promoted the formation of char residues at elevated temperatures. The FR activity was preserved even after an extensive water-leaching test, confirmed by the limiting oxygen index (LOI) and cone calorimetry. The reduction of fire hazards was achieved through the increase of the LOI to above 80%, reduction of 30% of the peak heat release rate (pHRR2), reduction of smoke production, and a longer ignition time. The modulus of elasticity of FR-modified wood increased by 40% without significantly decreasing the modulus of rupture.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2023
National Category
Wood Science Physical Chemistry
Research subject
Wood Science and Engineering; Structural Engineering; Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-95881 (URN)10.1021/acsomega.3c00146 (DOI)000960080200001 ()37008136 (PubMedID)2-s2.0-85150425157 (Scopus ID)
Funder
Swedish Research Council Formas, 2021-00818
Note

Validerad;2023;Nivå 2;2023-04-21 (joosat);

Funder: OP RDE (Grant no.CZ.02.1.01/0.0/0.0/16_019/0000803); CT WOOD, Luleå University of Technology

Licens fulltext: CC BY License

Available from: 2023-03-15 Created: 2023-03-15 Last updated: 2023-09-22Bibliographically approved
Hammond, O. S., Bousrez, G., Mehler, F., Li, S., Shimpi, M. R., Doutch, J., . . . Mudring, A.-V. (2023). Molecular Architecture Effects on Bulk Nanostructure in Bis(Orthoborate) Ionic Liquids. Small, 19(43), Article ID 2300912.
Open this publication in new window or tab >>Molecular Architecture Effects on Bulk Nanostructure in Bis(Orthoborate) Ionic Liquids
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2023 (English)In: Small, ISSN 1613-6810, E-ISSN 1613-6829, Vol. 19, no 43, article id 2300912Article in journal (Refereed) Published
Abstract [en]

A series of 19 ionic liquids (ILs) based on phosphonium and imidazolium cations of varying alkyl-chain lengths with the orthoborate anions bis(oxalato)borate [BOB]−, bis(mandelato)borate, [BMB]− and bis(salicylato)borate, [BScB]−, are synthesized and studied using small-angle neutron scattering (SANS). All measured systems display nanostructuring, with 1-methyl-3-n-alkyl imidazolium-orthoborates forming clearly bicontinuous L3 spongelike phases when the alkyl chains are longer than C6 (hexyl). L3 phases are fitted using the Teubner and Strey model, and diffusely-nanostructured systems are primarily fitted using the Ornstein-Zernicke correlation length model. Strongly-nanostructured systems have a strong dependence on the cation, with molecular architecture variation explored to determine the driving forces for self-assembly. The ability to form well-defined complex phases is effectively extinguished in several ways: methylation of the most acidic imidazolium ring proton, replacing the imidazolium 3-methyl group with a longer hydrocarbon chain, substitution of [BOB]− by [BMB]−, or exchanging the imidazolium for phosphonium systems, irrespective of phosphonium architecture. The results suggest there is only a small window of opportunity, in terms of molecular amphiphilicity and cation:anion volume matching, for the formation of stable extensive bicontinuous domains in pure bulk orthoborate-based ILs. Particularly important for self-assembly processes appear to be the ability to form H-bonding networks, which offer additional versatility in imidazolium systems.

Place, publisher, year, edition, pages
John Wiley and Sons Inc, 2023
Keywords
ionic liquids, nanostructures, orthoborates, small angle neutron scattering
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-99434 (URN)10.1002/smll.202300912 (DOI)001020697000001 ()37395635 (PubMedID)2-s2.0-85163735321 (Scopus ID)
Funder
Swedish Foundation for Strategic Research, “REFIT” project EM16-0013Knut and Alice Wallenberg Foundation, KAW2012.0078Swedish Research Council, 2018–05017, 2017–04080
Note

Validerad;2023;Nivå 2;2023-11-02 (joosat);

Licens fulltext: CC BY-NC License

Available from: 2023-08-10 Created: 2023-08-10 Last updated: 2023-11-02Bibliographically approved
Filippov, A. & Antzutkin, O. N. (2023). State of anion in ethylammonium nitrate enclosed between micrometer-spaced glass plates as studied by 17O and 15N NMR. Physical Chemistry, Chemical Physics - PCCP, 25(20), 14538-14545
Open this publication in new window or tab >>State of anion in ethylammonium nitrate enclosed between micrometer-spaced glass plates as studied by 17O and 15N NMR
2023 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 25, no 20, p. 14538-14545Article in journal (Refereed) Published
Abstract [en]

Some aprotic and protic ionic liquids (ILs) containing nitrate anion demonstrate unusual dynamic behavior of cations when these ILs are enclosed in micrometer-spaced layers between glass plates. We applied 17O and 15N NMR spectroscopy to discover the state and transformations of 17O and 15N isotopically enriched nitrate anion of ethylammonium nitrate (EAN) enclosed between glass plates. 15N NMR spectra demonstrated preferential orientation of the principal axes of the nitrate anions perpendicular to the normal of the glass surface. Therefore, isotropic ionic liquid EAN, when placed within a micrometer-spaced enclosure, forms an ordered phase, which is similar to a liquid crystal. The peculiarity of this phase is that the cations do not have a predominant orientation. Other features of this phase that are typical for liquid crystal phases are the changed local and translational dynamics in comparison with the isotropic state and slow transformation occurring under the action of an external magnetic field.

Place, publisher, year, edition, pages
RSC Publishing, 2023
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-97664 (URN)10.1039/d3cp01737k (DOI)000988042100001 ()37191082 (PubMedID)2-s2.0-85159653743 (Scopus ID)
Note

Validerad;2023;Nivå 2;2023-05-29 (joosat);

Funder: J. C. and Seth M. Kempe; Swedish Foundation for Strategic Research (project EM16-0013)

Licesn fulltext: CC BY License

Available from: 2023-05-29 Created: 2023-05-29 Last updated: 2023-09-05Bibliographically approved
Jain, P. & Antzutkin, O. (2022). 2-Ethylhexylsulfate Anion-based Surface-Active Ionic Liquids (SAILs) as Temperature Persistent Electrolytes for Supercapacitors. Journal of Ionic Liquids, 2(2), Article ID 100034.
Open this publication in new window or tab >>2-Ethylhexylsulfate Anion-based Surface-Active Ionic Liquids (SAILs) as Temperature Persistent Electrolytes for Supercapacitors
2022 (English)In: Journal of Ionic Liquids, ISSN 2772-4220, Vol. 2, no 2, article id 100034Article in journal (Refereed) Published
Abstract [en]

We report on a comparative study of three novel non-halogenated surface-active ionic liquids (SAILs), which contain a surface-active anion, 2-ethylhexyl sulfate ([EHS]−), and phosphonium or imidazolium cations: tetrabutylphosphonium ([P4,4,4,4]+), trihexyl(tetradecyl)phosphonium ([P6,6,6,14]+), and 1-methyl-3-hexylimidazolium ([C6C1Im]+). Thermal and electrochemical properties i.e., ionic conductivities at different temperatures and electrochemical potential windows of these SAILs were thoroughly studied. SAIL's electrochemical performance as electrolytes was also examined in a multi-walled-carbon- nanotubes (MWCNT)-based supercapacitor over a wide range of temperatures from 253 to 373 K. We observed that the electrode material in the supercapacitor cell with [C6C1Im][EHS] as an electrolyte has a higher specific capacitance (Celec in F g−1), a higher electric energy density (E in W h kg−1), and a higher electric power density (P in kW kg−1) as compared to the other studied SAILs, [P4,4,4,4][EHS], [P6,6,6,14][EHS] and [N8,8,8,8][EHS] (from our preceding study) in a temperature range from 253 to 373 K: At the scan rate of 2 mV s−1 a supercapacitor cell with a MWCNT-based electrode and [C6C1Im][EHS], [P4,4,4,4][EHS] and [P6,6,6,14][EHS] as electrolytes has the specific capacitance, Celec = 148, 90 and 47 F g−1 and the energy density, E = 82, 50 and 26 W h kg−1, respectively, when measured at 298 K. For the named three SAILs at the scan rate of 2 mV s−1, a two- to three-fold increase in the specific capacitance and the energy density values was measured at 373 K: Celec = 290, 198 and 114 F g−1 and E = 161, 110 and 63 Wh kg−1, respectively. The solution resistance (Rs), charge transfer resistance (Rct) and equivalent series resistance (ESR) all decreased two- to three-fold with an increase in temperature from 298 to 373 K. With the high specific capacitance and enhanced energy and power density and wider electrochemical potential window as compared to the molecular organic and aqueous electrolytes, these SAILs can be used for high-temperature electrochemical applications, such as high power and energy storage devices. In particular, up to now, [C6C1Im][EHS] and [P4,4,4,4][EHS] are the most appropriate candidates for such applications.

Place, publisher, year, edition, pages
Elsevier, 2022
Keywords
Non-halogenated ionic liquids, Surface-active ionic liquids, Specific capacitance, Electric energy density, Electric power density
National Category
Condensed Matter Physics Physical Chemistry Energy Systems
Research subject
Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-90876 (URN)10.1016/j.jil.2022.100034 (DOI)2-s2.0-85146741544 (Scopus ID)
Funder
The Kempe Foundations, JCK-1810, SMK-1945, JCK-1306, JCK-1433Luleå University of TechnologySwedish Foundation for Strategic Research, EM16-003, 2019-2023
Note

Godkänd;2022;Nivå 0;2022-06-30 (joosat);

Available from: 2022-06-02 Created: 2022-06-02 Last updated: 2023-10-11Bibliographically approved
Filippov, A., Antzutkin, O. N., Arkhipov, V. P. & Gnezdilov, O. I. (2022). Diffusivity of ethylammonium nitrate protic ionic liquid confined in porous glasses. Journal of Molecular Liquids, 356, Article ID 118998.
Open this publication in new window or tab >>Diffusivity of ethylammonium nitrate protic ionic liquid confined in porous glasses
2022 (English)In: Journal of Molecular Liquids, ISSN 0167-7322, E-ISSN 1873-3166, Vol. 356, article id 118998Article in journal (Refereed) Published
Abstract [en]

We studied the diffusion of ionic liquid ethylammonium nitrate confined within pores of two types of porous glass, Vycor and Varapor, with average pore sizes of 4 nm and 9.8 nm, respectively, by 1H NMR in the temperature range of 295–325 K. The diffusional behavior of the ionic liquid corresponds to long-term diffusion in a system of interconnected pores. It was shown that the diffusivity of EAN confined in Varapor is controlled by the porous system’s tortuosity and does need to take into consideration the interaction with the surface of the discrete pore walls. In the case of Vycor, the long-term diffusivity is a factor 1.5 lower than that expected in the absence of interaction with the pore walls. Two possible mechanisms that may explain this discrepancy are the EAN-surface interaction and retardation of EAN diffusion compared to n-decane in smaller pores present in Vycor porous glass due to pore size distribution. Confinement of EAN in nanoporous glass does not leads to the EAN phase transformation observed earlier for alkylammonium nitrates enclosed in a micrometer-sized layer. Prolonged exposure of EAN to a strong static magnetic field does not leads to changes in the NMR and diffusivity of EAN over time.

Place, publisher, year, edition, pages
Elsevier, 2022
Keywords
Ionic liquid, Self-diffusion, Tortuosity, Ion dynamics, Interaction with pores
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-90050 (URN)10.1016/j.molliq.2022.118998 (DOI)000820287800006 ()2-s2.0-85127267025 (Scopus ID)
Note

Validerad;2022;Nivå 2;2022-04-01 (hanlid);

Funder: Kazan Federal University (0671-2020-0051)

Available from: 2022-04-01 Created: 2022-04-01 Last updated: 2023-09-05Bibliographically approved
Filippov, A., Gnezdilov, O. I. & Antzutkin, O. N. (2022). Dynamics of ethylammonium nitrate near PTFE surface. Magnetic Resonance Imaging, 85, 102-107
Open this publication in new window or tab >>Dynamics of ethylammonium nitrate near PTFE surface
2022 (English)In: Magnetic Resonance Imaging, ISSN 0730-725X, E-ISSN 1873-5894, Vol. 85, p. 102-107Article in journal (Refereed) Published
Abstract [en]

Self-diffusion of ions in the protic ionic liquid ethylammonium nitrate (EAN) was studied by 1H NMR pulsed field gradient techniques between 294 and 393 K in the presence of a PTFE insert in a 5-mm NMR tube. At all temperatures, the bulk diffusion of ions (measured by 1H and 15N NMR) can be described by a unique diffusion coefficient. The presence of solid hydrophobic surfaces of PTFE induces regions of EAN in their vicinity, where diffusion of ions, both cations and anions, is reduced compared to the bulk values. An additional line-shape analysis in 1H NMR spectra showed that local mobility of ethylammonium cations in the surface layers near PTFE is also reduced.

Place, publisher, year, edition, pages
Elsevier, 2022
Keywords
Ionic liquid, Solid-liquid interface, Pulsed-field gradient, NMR diffusometry, Ion dynamics
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-87585 (URN)10.1016/j.mri.2021.10.022 (DOI)000712140600014 ()34678437 (PubMedID)2-s2.0-85117691057 (Scopus ID)
Funder
Stiftelsen Seth M. Kempes Minnes StipendiefondLuleå University of Technology
Note

Validerad;2021;Nivå 2;2021-10-25 (beamah);

Forskningsfinansiär: Kazan Federal University Strategic Academic Leadership Program

Available from: 2021-10-21 Created: 2021-10-21 Last updated: 2023-09-05Bibliographically approved
Rusanova-Naydenova, D., Trublet, M., Klysubun, W., Cholsuk, C., Iuga, D., Dupree, R., . . . Persson, I. (2022). Synthesis and structural characterisation of solid titanium(iv) phosphate materials by means of X-ray absorption and NMR spectroscopy. Dalton Transactions, 51(21), 8192-8207
Open this publication in new window or tab >>Synthesis and structural characterisation of solid titanium(iv) phosphate materials by means of X-ray absorption and NMR spectroscopy
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2022 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 51, no 21, p. 8192-8207Article in journal (Refereed) Published
Abstract [en]

Solid titanium phosphate, TiP, materials hold great promise for wastewater treatment for removal of metal ions and complexes. A series of TiP materials, synthesised at mild conditions and short reaction times, have been structurally characterised using solid-state X-ray absorption spectroscopy, phosphorus and titanium K edge XANES and EXAFS, and 31P and 47/49Ti NMR spectroscopy. The titanium K edge EXAFS data of α-Ti(HPO4)2·H2O (α-TiP) revealed octahedral coordination of oxygens around titanium. Repeated washing of primary β-/γ-TiP with hydrochloric acid results in formation of a weakly ordered solid, TiO(OH)(H2PO4)·H2O, TiP1-H. The structure of TiP1-H is shown by Ti EXAFS to be a titanyl compound, containing a short Ti O bond. The analogous data for linked titanium phosphate compounds (LTP) disclosed that inter-linkage occurs between α-TiP and titanyl phosphate units, supported by 31P–31P NOESY NMR data. 47/49Ti NMR and Ti pre-edge XANES show evidence of two different titanium environments in LTP, one very similar to that observed in TiP1-H and a second more symmetric octahedral environment. Data are discussed in terms of induced acidic hydrolyses of titanium(IV) and phosphate counterpart during washings with hydrochloric acid and water. A straightforward relation between synthesis parameters/post synthetic treatment and structural re-arrangement in the materials is established.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2022
National Category
Materials Chemistry
Research subject
Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-90682 (URN)10.1039/d2dt00902a (DOI)000797039400001 ()35583237 (PubMedID)2-s2.0-85132007265 (Scopus ID)
Funder
European Regional Development Fund (ERDF)The Kempe Foundations, JCK-1306 and JCK-1433Swedish Research Council for Environment, Agricultural Sciences and Spatial PlanningWallenberg Foundations
Note

Validerad;2022;Nivå 2;2022-05-31 (joosat);

Funder: EPSRC and BBSRC (grant no. EP/T015063/1); University of Warwick; Advantage West Midlands (AWM)

Available from: 2022-05-20 Created: 2022-05-20 Last updated: 2023-09-05Bibliographically approved
Loseva, O. V., Rodina, T. A., Shah, F. U., Smolentsev, A. I., Antzutkin, O. N. & Ivanov, A. V. (2022). Two structural types of dithiocarbamato-chlorido complexes of mercury(II): Preparation, supramolecular self-assembly, solid-state 13C and 15N NMR characterisation and thermal behaviour of pseudo-polymeric compounds of [Hg2(S2CNBu2)2Cl2] and [Hg4(S2CNiBu2)6][Hg2Cl6]. Inorganica Chimica Acta, 533, Article ID 120786.
Open this publication in new window or tab >>Two structural types of dithiocarbamato-chlorido complexes of mercury(II): Preparation, supramolecular self-assembly, solid-state 13C and 15N NMR characterisation and thermal behaviour of pseudo-polymeric compounds of [Hg2(S2CNBu2)2Cl2] and [Hg4(S2CNiBu2)6][Hg2Cl6]
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2022 (English)In: Inorganica Chimica Acta, ISSN 0020-1693, E-ISSN 1873-3255, Vol. 533, article id 120786Article in journal (Refereed) Published
Abstract [en]

Two new crystalline dithiocarbamato-chlorido complexes of mercury(II), [Hg2{S2CN(C4H9)2}2Cl2] (1) and [Hg4{S2CN(iso-C4H9)2}6][Hg2Cl6] (2), have been prepared and chemically identified by solution (1H, 13C) NMR and solid-state (13C, 15N) CP-MAS NMR and FT-IR spectroscopy. The crystal, molecular and supramolecular structures of these compounds were established using single-crystal X-ray diffraction (XRD) analysis. The obtained complexes reveal two principally different types of structural organisation. In the structure of the former neutral complex, there are two isomeric doubly-bridged binuclear molecules [Hg2(S2CNBu2)2Cl2] (‘A’ and ‘B’), whereas the latter compound comprises two ionic structural moieties: the tetranuclear cation [Hg4(S2CNiBu2)6]2+ and the binuclear anion [Hg2Cl6]2−. In both ionic units, pairs of iBu2Dtc or chloride ligands, which perform a bridging structural function, combine with neighbouring mercury atoms. In turn, intermolecular/interionic secondary interactions Hg···S/Hg···Cl are involved in the formation of supramolecular structures of complexes 1/2, yielding pseudo-polymeric chains of (···‘A’···‘B’···)n/(···[Hg4(S2CNiBu2)6]···[Hg2Cl6]···)n, which exhibit alternation of isomeric molecules of 1/ionic moieties of 2 along their lengths. Despite the significant structural difference between the above complexes, we established, using simultaneous thermal analysis (STA), that both exhibit very similar thermal behaviour. Moreover, during the thermal transformations of both compounds 1 and 2, the same two substances are generated: HgCl2 and HgS.

Place, publisher, year, edition, pages
Elsevier, 2022
Keywords
Heteroleptic dithiocarbamato-chlorido mercury(II) complexes, Pseudo-polymer compounds, Supramolecular self-assembly, Secondary (Hg...S, Hg...Cl) interactions, Solid-state heteronuclear (13C, 15N) CP-MAS, NMR spectroscopy, Thermal transformation of substances
National Category
Inorganic Chemistry
Research subject
Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-88623 (URN)10.1016/j.ica.2021.120786 (DOI)000741684300002 ()2-s2.0-85122295539 (Scopus ID)
Funder
Knut and Alice Wallenberg FoundationSwedish Foundation for Strategic Research, EM16-0013
Note

Validerad;2022;Nivå 2;2022-01-21 (johcin)

Available from: 2021-12-30 Created: 2021-12-30 Last updated: 2023-09-05Bibliographically approved
Korneeva, E. V., Smolentsev, A. I., Antzutkin, O. & Ivanov, A. V. (2021). A novel silver(I) di-iso-butyldithiocarbamate: Unusually complicated 1-D polymeric structure, multiple ligand-supported Ag–Ag interactions and its capability to bind gold(III). Preparation, structural organisation and (13C, 15N) CP-MAS NMR of [Ag6(S2CNiBu2)6]n and [Au(S2CNiBu2)2][AgCl2]. Inorganica Chimica Acta, 525, Article ID 120383.
Open this publication in new window or tab >>A novel silver(I) di-iso-butyldithiocarbamate: Unusually complicated 1-D polymeric structure, multiple ligand-supported Ag–Ag interactions and its capability to bind gold(III). Preparation, structural organisation and (13C, 15N) CP-MAS NMR of [Ag6(S2CNiBu2)6]n and [Au(S2CNiBu2)2][AgCl2]
2021 (English)In: Inorganica Chimica Acta, ISSN 0020-1693, E-ISSN 1873-3255, Vol. 525, article id 120383Article in journal (Refereed) Published
Abstract [en]

We have synthesised three new complexes of [Ag6{S2CN(iso-C4H9)2}6]n (1), [Au{S2CN(iso-C4H9)2}2][AgCl2] (2) and [Au{S2CN(iso-C4H9)2}2][Ag0.69Au0.31Cl2] (3), chemically identified these compounds using solution (1H, 13C) and solid-state (13C, 15N) CP-MAS NMR and FT-IR spectroscopy, and structurally characterised them by single-crystal X-ray diffraction analysis. There are six structurally inequivalent silver(I) centres in the former compound, whose unusually complicated, monodimensional polymeric structure is generally stabilised by six unequal iBuDtc ligands acting as bridges, along with numerous ligand-supported Ag–Ag interactions. Studying the capability of the precipitated AgiBuDtc to bind gold(III) from a [AuCl4]/5.15 M NaCl solution, the double pseudo-polymeric heterometallic dithiocarbamato-chlorido complexes 2 and 3 were successfully obtained as individual fixation modes of gold to the solid phase. In the self-assembly of a bidimensional supramolecular structure of the latter two compounds, numerous interionic secondary bonds (Au···S, Ag···S and S···Cl), the anagostic H–C···Ag interactions and the Cl···H–C hydrogen bonds play a key role. To study the thermal behaviour of crystalline compounds 1 and 2, we additionally used simultaneous thermal analysis (STA). During the thermolysis of 1/2, the formation of Ag2S/AgCl,Au0 was supported, respectively, by energy dispersive X-ray (EDX) spectroscopy, while the dispersity and morphology of residual substances were studied using scanning electron microscopy.

Place, publisher, year, edition, pages
Elsevier, 2021
Keywords
Polymeric silver(I) di-iso-butyldithiocarbamate, Ligand-supported argentophilic interaction, Pseudo-polymer gold(III)-silver(I) complex, Supramolecular self-assembly, Heteronuclear (13C, 15N) CP-MAS NMR
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
Identifiers
urn:nbn:se:ltu:diva-83686 (URN)10.1016/j.ica.2021.120383 (DOI)000675723400005 ()2-s2.0-85109449668 (Scopus ID)
Funder
Knut and Alice Wallenberg FoundationSwedish Foundation for Strategic Research The Kempe Foundations
Note

Validerad;2021;Nivå 2;2021-07-01 (beamah)

Available from: 2021-04-15 Created: 2021-04-15 Last updated: 2023-09-05Bibliographically approved
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