Engineering topics
Abboud, Khalil A.
Publications and source records attributed to Abboud, Khalil A..
iClick synthesis of network metallopolymers
Described is an approach to preparing the first iClick network metallopolymers with porous properties. Treating digoldazido complex 2-AuN 3 with trigoldacetylide 3-AuPPh 3 or 3-AuPEt 3 , trialkyne 3-H, tetragoldacetylide 4-AuPPh 3 , or tetraalkyne 4-H in CH 2 Cl 2 affords five iClick network metallopolymers 5-AuPPh 3 , 5-AuPEt 3 , 5-H, 6-AuPPh 3 , and 6-H. Additionally, confirmation of the iClick network metallopolymers comes from FTIR, 13 C solid-state cross-coupling magic angle spinning (CPMAS) NMR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and nitrogen and CO 2 sorption analysis. Employing model complexes 7-AuPPh 3 , 7-AuPEt 3 , 7-H, 8-AuPPh 3 , and 8-H provides structural insights due to the insolubility of iClick network metallopolymers.
Analysis of spin frustration in an Fe III 7 cluster using a combination of computational, experimental, and magnetostructural correlation methods
The synthesis, structure, and magnetic properties are reported for [Fe 7 O 3 (O 2 C t Bu) 9 (mda) 3 (H 2 O) 3 ] ( 1 ), where mdaH 2 is N -methyldiethanolamine. 1 was prepared from the reaction of [Fe 3 O(O 2 C t Bu) 6 (H 2 O) 3 ](NO 3 ) with mdaH 2 in a 1:~3 ratio in MeCN. The core of 1 consists of a central octahedral Fe III ion held within a non-planar Fe 6 loop by three μ 3 -O 2- and three μ 2 -RO - arms from the three mda 2- chelates. Variable-temperature dc and ac magnetic susceptibility studies revealed dominant antiferromagnetic coupling, leading to a ground state spin of S = 5 / 2 . The ground state was confirmed by a fit of magnetization data collected in the 0.1–7.0 T and 1.8–10.0 K ranges. The four Fe 2 pairwise exchange parameters ( J 1 - J 4 ) were estimated by independent methods: theoretical calculations using either broken symmetry energy differences (-46.3, -16.2, -3.9, and - 28.1 cm -1 , respectively) or Green’s function approximation methods (-41.4, -14.8, -13.2, and - 24.7 cm -1 ), and a magnetostructural correlation (MSC) previously developed for high nuclearity Fe III /O complexes (-39.5, -13.8, -6.7, and - 23.5 cm -1 ). Additionally, the J 1 - J 4 obtained from the MSC and theoretical methods were used with the program PHI to both simulate χ M T vs T as well as to serve as reasonable input values to fit the experimental data (-41.0, -11.4, -5.0, and - 27.3 cm -1 ). Analysis of the J ij led to identification of the spin frustration effects operative and the resultant spin vector alignments at each Fe III ion, thus allowing for the rationalization of the experimental ground state.
SPAAC iClick: progress towards a bioorthogonal reaction in-corporating metal ions
Combining strain-promoted azide–alkyne cycloaddition (SPAAC) and inorganic click (iClick) reactivity provides access to metal 1,2,3-triazolates.
Exchange-biased quantum tunnelling of magnetization in a [Mn 3 ] 2 dimer of single-molecule magnets with rare ferromagnetic inter-Mn 3 coupling
A covalently-linked dimer of two single-molecule magnets (SMMs), [Mn 6 O(O 2 CMe) 6 (1,3-ppmd) 3 ](ClO 4 ) 2 , has been synthesized from the reaction of [Mn 3 O(O 2 CMe) 6 (py) 3 ](ClO 4 ) with 1,3-phenylene-bis(pyridin-2-ylmethanone) dioxime (1,3-ppmdH 2 ). It contains two [Mn III 3 O] +7 triangular units linked by three 1,3-ppmd 2 - groups into an [Mn 3 ] 2 dimer with D 3 symmetry. Solid-state dc and ac magnetic susceptibility measurements showed that each Mn 3 subunit retains its properties as an SMM with an S = 6 ground state. Magnetization vs. dc field sweeps on a single crystal reveal hysteresis loops below 1.3 K exhibiting exchange-biased quantum tunnelling of magnetization (QTM) steps with a bias field of +0.06 T. This is the first example of a dimer of SMMs showing a positive exchange bias of the QTM steps in the hysteresis loops, and it has therefore been subjected to a detailed analysis. Simulation of the loops determines that each Mn3 unit is exchange-coupled with its neighbour primarily through the 1,3-ppmd 2 - linkers, confirming a weak ferromagnetic inter-Mn 3 interaction of J 12 ≈ +6.5 mK ($\hat{H}= -2J\hat{S}_i·\hat{S}_j$ convention). High-frequency EPR studies of a microcrystalline powder sample enable accurate determination of the zero-field splitting parameters of the uncoupled Mn3 SMMs, while also confirming the weak exchange interaction between the two SMMs within each [Mn 3 ] 2 dimer. The combined results emphasize the ability of designed covalent linkers to generate inter-SMM coupling of a particular sign and relative magnitude, and thus the ability of such linkers to modulate the quantum physics. As such, this article supports the feasibility of using designed covalent linkers to develop molecular oligomers of SMMs, or other magnetic molecules, as multi-qubit systems and/or other components of new quantum technologies.
Extending the family of reduced [Mn 12 O 12 (O 2 CR) 16 (H 2 O) x ] n- complexes, and their sensitivity to environmental factors
Here, the family of reduced [Mn 12 O 12 (O 2 CR) 16 (H 2 O) 4 ] n- (n = 1, 2) single-molecule magnets (SMMs) has been expanded with the synthesis of new members using I - as a stoichiometric one-electron reducing agent of the neutral n = 0 complexes. Electrochemical data, 1 H NMR spectra of the [Mn 12 O 12 (O 2 CCH 2 Cl) 16 (H 2 O) 3 ] 0,-,2- salts, and the crystal structures of two complexes, (PPh 4 )[Mn 12 O 12 (O 2 CCHCl 2 ) 16 (H 2 O) 4 ] and (PPh 4 ) 2 [Mn 12 O 12 (O 2 CCH 2 Cl) 16 (H 2 O) 3 ] have been obtained. For (PPh 4 ) 2 [Mn 12 O 12 (O 2 CCH 2 Cl) 16 (H 2 O) 3 ], the data confirm an S = 10 ground state, and magnetization vs dc field scans on a pristine crystal exhibit hysteresis loops possessing steps due to quantum tunneling of magnetization (QTM). In addition, two forms of the cluster have been identified in the crystal with distinctly different relaxation barriers, with the faster-relaxing form being the majority one in pristine crystals from mother liquor, and the slower-relaxing one becoming the majority one in vacuum-dried samples. Similar behavior is seen for (PPh 4 )[Mn 12 O 12 (O 2 CCHCl 2 ) 16 (H 2 O) 4 ] with an S = 19 / 2 ground state, which shows three forms to be present in the hysteresis loops of a pristine crystal, all converting to a slow-relaxing form on vacuum-drying. High-frequency EPR spectra of the latter confirm a high axial anisotropy with $\mathcal{D}$ = -0.477 cm -1 and rationalize its effective relaxation barrier U eff = 57 K. The combined work emphasizes a high sensitivity of such ultra-small nanomagnets to environmental influences, affecting their properties significantly, especially their quantum properties that are so important to many potential new 21st century applications.
Iron(III)–Oxo Cluster Chemistry with Dimethylarsinate Ligands: Structures, Magnetic Properties, and Computational Studies
A program has been initiated to develop Fe III /oxo cluster chemistry with the ‘pseudo-carboxylate’ ligand dimethylarsinate (Me 2 AsO 2 - ) for comparison with the well investigated Fe III /oxo/carboxylate cluster area. The synthesis and characterization of three polynuclear Fe III complexes are reported, [Fe 12 O 4 (O 2 C t Bu) 8 (O 2 AsMe 2 ) 17 (H 2 O) 3 ]Cl 3 (1), Na 2 [Fe 12 Na 2 O 4 (O 2 AsMe 2 ) 20 (NO 3 ) 6 (Me 2 AsO 2 H) 2 (H 2 O) 4 ](NO 3 ) 6 (2) and [Fe 3 (O 2 AsMe 2 ) 6 (Me 2 AsO 2 H) 2 (hqn) 2 ](NO 3 ) (3), where hqn is 8-hydroxyquinoline. The Fe 12 core of 1 is a type never previously encountered in Fe III carboxylate chemistry, consisting of two Fe 6 units each of which comprises two {Fe 3 (μ 3 -O 2- )} units bridged by three Me 2 AsO 2 - groups and linked into an Fe 12 loop structure by two anti-anti η 1 :η 1 :μ Me 2 AsO 2 - groups, a bridging mode extremely rare with carboxylates. 2 also consists of two Fe 6 units, differing in their ligation from those in 1, and this time linked together into a linear structure by a central {Na 2 (NO 3 ) 2 } bridging unit. 3 is a linear Fe 3 complex with no monoatomic bridges between Fe III ions, a very rare situation in Fe III chemistry with any ligands, and unprecedented in Fe carboxylate chemistry. The distinct differences observed in arsinate vs carboxylate ligation modes are rationalized largely based on the greater basicity of the former vs the latter. Variable-temperature dc and ac magnetic susceptibility data reveal all Fe 2 pairwise interactions to be antiferromagnetic. For 1 and 2, the different J ij couplings were estimated by use of a magnetostructural correlation for high nuclearity Fe III -oxo clusters and by density functional theory calculations using broken symmetry methods, allowing identification of their relative spin vector alignments and thus rationalization of their S = 0 ground states. The J ij values were then used as input values to give excellent fits of the experimental χM T vs T data. For 3, the fits of the experimental χM T vs T data to the Van Vleck equation or with PHI gave a very weak J 12 = -0.8(1) cm -1 (H = –2JŠ i ·Š j convention) between adjacent Fe III ions, and an S = 5/2 ground state. Furthermore, these initial Fe III arsinate complexes also provide structural parameters that help validate literature assignments of arsinate binding modes to iron oxide/hydroxide minerals as part of environmental concerns of using arsenic-containing herbicides in agriculture.