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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Levason, William
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (25/25 displayed)
- 2022Tungsten(VI) selenide tetrachloride, WSeCl 4 - synthesis, properties, coordination complexes and application of [WSeCl 4 (SenBu 2 )] for CVD growth of WSe 2 thin filmscitations
- 2021Mono- and di-phosphine oxide complexes of aluminium, gallium and indium with weakly coordinating triflate anions – Synthesis, structures and propertiescitations
- 2021Tungsten disulfide thin films via electrodeposition from a single source precursorcitations
- 2020Selective chemical vapor deposition approach for Sb2Te3 thin film micro-thermoelectric generatorscitations
- 2020Improved thermoelectric performance of Bi2Se3 alloyed Bi2Te3 thin films via low pressure chemical vapour depositioncitations
- 2020Improved thermoelectric performance of Bi 2 Se 3 alloyed Bi 2 Te 3 thin films via low pressure chemical vapour depositioncitations
- 2018Electrodeposition of a functional solid state memory material – germanium antimony telluride from a non-aqueous plating bathcitations
- 2016Haloplumbate salts as reagents for the non-aqueous electrodeposition of leadcitations
- 2016A versatile precursor system for supercritical fluid electrodeposition of main-group materialscitations
- 2016Nanoscale arrays of antimony telluride single crystals by selective chemical vapor depositioncitations
- 2015Chemical vapour deposition of antimony chalcogenides with positional and orientational control: precursor design and substrate selectivitycitations
- 2015Aza-macrocyclic complexes of Group 1 cations:synthesis, structures and density functional theory studycitations
- 2015Non-aqueous electrodeposition of functional semiconducting metal chalcogenides: Ge2Sb2Te5phase change memorycitations
- 2015A Versatile Precursor System for Supercritical Fluid Electrodeposition of Main-Group Materialscitations
- 2015Phase-change memory properties of electrodeposited Ge-Sb-Te thin filmcitations
- 2014Niobium(v) and tantalum(v) halide chalcogenoether complexes – towards single source CVD precursors for ME2thin filmscitations
- 2013Non-aqueous electrodeposition of metals and metalloids from halometallate saltscitations
- 2013Low pressure chemical vapour deposition of crystalline Ga2Te3 and Ga2Se3 thin films from single source precursors using telluroether and selenoether complexescitations
- 2013Telluroether and selenoether complexes as single source reagents for low pressure chemical vapor deposition of crystalline Ga2Te3 and Ga2Se3 thin filmscitations
- 2013Chromium(V) oxide trichloride, and some pentachlorido-oxido-chromate(V) salts: structures and spectroscopic characterizationcitations
- 2012Highly selective chemical vapor deposition of tin diselenide thin films onto patterned substrates via single source diselenoether precursorscitations
- 2011Chemical vapor deposition of GaP and GaAs thin films from [nBu2Ga(µ-EtBu2)2GanBu2] (E= P or As) and Ga(PtBu2)3citations
- 2010Synthesis and structure of [{C7F15CO2}2AgAu(PPh3)]2 and its use in electrodeposition of gold–silver alloyscitations
- 2009Spectroscopic and Vanadium K-Edge EXAFS Studies on VO2Cl and the Crystal Structure of [{Cl2VO(O2PCl2)(POCl3)}2]citations
- 2009Electrodeposition of metals from supercritical fluidscitations
Places of action
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article
Aza-macrocyclic complexes of Group 1 cations:synthesis, structures and density functional theory study
Abstract
The Group 1 complexes, [M(Me6[18]aneN6)][BArF] (M = Li–Cs; Me6[18]aneN6 = 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane; BArF = tetrakis{3,5-bis(trifluoromethyl)-phenyl}borate), are obtained in high yield by reaction of the macrocycle with M[BArF] in anhydrous CH2Cl2 solution, and characterised spectroscopically (1H, 13C{1H}, 7Li, 23Na, and 133Cs NMR), by microanalysis and, for M = Li, K, and Rb, by single crystal X-ray analysis. The structures show N6-coordination to the metal ion; the small ionic radius for Li+ leads to a puckered conformation. In contrast, the K+ ion fits well into the N6 plane, with the [BArF]? anions above and below, leading to two K+ species in the asymmetric unit (a hexagonal planar [K(Me6[18]aneN6)]+ cation and a ‘[K(Me6[18]aneN6)(?1-BArF)2]? anion’, with long axial K?F interactions). The Rb+ ion sits above the N6 plane, with two long axial Rb?F interactions in one cation and two long, mutually cis Rb?F interactions in the other. The unusual sandwich cations, [M(Me3tacn)2]+ (M = Na, K; distorted octahedral, N6 donor set) and half-sandwich cations [Li(Me3tacn)(thf)]+ (distorted tetrahedron, N3O donor set), [Li(Me4cyclen)(OH2)]+, and [Na(Me4cyclen)(thf)]+ (both distorted square pyramids with N4O donor sets) were also prepared (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane, Me4cyclen = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). Density functional theory (DFT) calculations, using the BP86 and B3LYP functionals, show that the accessibility of the [M(Me3tacn)2]+ sandwich cations depends strongly on the M+ ionic radius, such that it is sufficiently large to avoid steric clashing between the Me groups of the two rings, and small enough to avoid very acute N–M–N chelate angles. The calculations also show that coordination to the Group 1 cation involves significant donation of electron density from the p-orbitals on the N atoms of the macrocycle, rather than purely electrostatic interactions.