Search Results (11)

Tetranuclear rhodium carbonyl clusters are vital catalytic precursors; yet derivatives featuring bidentate phosphines are less common, due to the propensity for cluster fragmentation during synthesis. This study reports the successful isolation of five new heteroleptic species by reacting Rh₄(CO)₁₂ with various bidentate diphosphines under homogeneous conditions and at room temperature, namely the mono-substituted Rh₄(CO)₁₀(dppe) (1) and Rh₄(CO)₁₀(dppb) (3), the rare bis-substituted derivative Rh₄(CO)₈(dppe)₂ (2), and the two unique dimeric assemblies {Rh₄(CO)₁₀(dpp-hexane)}₂ (4) and {Rh₄(CO)₁₀(trans-dppe)}₂ (5). The tetrahedral Rh₄ core of the cluster precursor was preserved in all cases. The new compounds were characterized via infrared (IR) spectroscopy and single-crystal X-ray diffraction (SC-XRD). Furthermore, variable-temperature (VT) ³¹P{¹H} NMR spectroscopy elucidated the dynamic behavior of the phosphorus atoms. This work reports a robust methodology for accessing stable, low-nuclearity rhodium phosphine clusters with tunable properties. Full article

We report the synthesis, spectroscopic, structural, and ultrafast photophysical investigation of a series of homoleptic and heteroleptic Zn(II) complexes based on the donor-acceptor β-diketonate ligand 4,4,4-trifluoro-1-phenylbutane-1,3-dione. Mass spectrometry, infrared, and NMR analyses confirm complexation and indicate possible fragmentation pathways involving the sequential loss of β-diketonate ligands. Single-crystal X-ray diffraction revealed that all complexes adopt monomeric octahedral geometries, with the ancillary nitrogen-based ligands introducing variable distortions. Thermal analyses confirmed that the complexes are non-volatile and have an onset >250 °C, with thermal decomposition primarily to ZnO and ZnF₂. Complexes with aromatic Lewis base led to higher residue percentages, likely due to the final graphitic carbon content. UV-Vis absorption and femtosecond transient absorption spectroscopy demonstrate that the chelated β-diketonate ring serves as the main optically active chromophore, a property unaffected by the nitrogen ligands. The free ligand undergoes rapid internal conversion, whereas coordination to Zn stabilizes the triplet state via LMCT, producing long-lived and chemically reactive species relevant to dissociation processes. This study demonstrates how tailored ligand environments can be exploited to tune excited-state properties, offering a rational framework for the design of functional precursors suitable for nonlinear photolysis and advanced nanomaterial synthesis. Full article

In this paper, four heteroleptic Ce(III) complexes, including Ce(thd)₃-phen (thd = 2,2,6,6-tetramethyl-3,5-heptanedione, phen = 1, 10—phenanthroline (1), Ce(thd)₃-MEDA (MEDA = N—Methylethylenediamine (2), Ce(thd)₃-MOMA (MOMA = N-(2-Methoxyethyl)methylamine (3), and Ce(thd)₃-DMDE (DMDE = N,N″-dimethyl ethanol amine (4), were synthesized and characterized with ¹H-NMR, elemental analysis, and X-ray single-crystal diffraction. The thermogravimetric analysis and vapor pressure results indicated that the complexing ability of a nitrogen-containing bidentate ligand with a cerium ion was stronger than that of a mixed oxygen-nitrogen-containing bidentate ligand. Complex 2 was selected as an ALD precursor to deposit a CeO₂ film on a SiO₂/Si (100) wafer. The self-limited deposition results demonstrated that complex 2 was a potential ALD precursor. Full article

The N-oxide functional group has been exploited for synthetic strategies and drug design, and it has been utilized in imaging agents. Herein, we present rare examples of neutral heteroleptic cyclometallated Ir(III) compounds that contain an uncoordinated N-oxide functional group. These species, along with others described within, were verified by NMR, EA, HRMS, and single-crystal X-ray analysis. N-oxide-containing Ir(III) species were prepared selectively in high yields > 66% from chloro-bridged Ir(III) dimers with Acipimox, a picolinate-type ligand containing the N-oxide functional group. Non-N-oxide analogs were synthesized in a similar fashion (yields > 77%). Electrochemical comparison (cyclic voltammetry) indicates that the presence of an N-oxide functional group anodically shifts the reduction potential, suggesting that the N-oxide is acting as an electron-withdrawing group in these species. Crystallographic studies were pursued to examine the coordination behavior of these N-oxides compared to their non-oxidized congeners. The Ir(III) complexes with Acipimox indeed leave the N-oxide uncoordinated and exposed on the complexes. The uncoordinated N-oxide group is influential in directing the packing structures of these complexes directly through C-H···O and O···π interactions at the N-oxide. The crystallographic characterization of cationic Ir(III) compounds with uncoordinated nitrogen atoms is also presented. The C-H···N interactions between these complexes form a variety of dimers, finite chains, and continuous chains. Future work will focus on functionalizing the cationic Ir(III) species into their corresponding N-oxide derivatives and rigorously characterizing how the N-oxide functional group impacts the optical properties of transition metal compounds in both cationic and neutral complexes. Full article

Hafnium oxide (HfO₂) is widely recognized as one of the most promising high-k dielectric materials due to its remarkable properties such as high permittivity, wide band gap, and excellent thermal and chemical stability. The atomic layer deposition (ALD) of HfO₂ has attracted significant attention in recent decades since it enables uniform and conformal deposition of HfO₂ thin films on various substrates. In this study, we examined the initial surface reactions of a series of homoleptic hafnium precursors on hydroxylated Si(100) surfaces using density functional theory calculations. Our theoretical findings align with previous experimental studies, indicating that hafnium amides exhibit higher reactivity compared to other precursors such as hafnium alkoxides and hafnium halides in surface reactions. Interestingly, we found that the chemisorption and reactivity of hafnium precursors are considerably affected by their thermal stability and size. For alkoxide precursors, which have similar thermal stabilities, the size of alkoxide ligands is an important factor in determining their reactivity. Conversely, the reactivity of hafnium halides, which have ligands of similar sizes, is primarily governed by their thermal stability. These insights are valuable for understanding the surface reaction mechanisms of precursors on hydroxylated Si(100) surfaces and for designing new materials, particularly heteroleptic precursors, in future research. Full article

Cu^2+/1+ complexes facilitate the reduction of CO₂ to valuable chemicals. The catalytic conversion likely involves the binding of CO₂ and/or reduction intermediates to Cu^2+/1+, which in turn could be influenced by the electron density on the Cu^2+/1+ ion. Herein we investigated whether modulating the redox potential of Cu^2+/1+ complexes by changing their ligand structures influenced their CO₂ reduction performance significantly. We synthesised new heteroleptic Cu^2/1+ complexes, and for the first time, studied a (Cu-bis(8-quinolinolato) complex, covering a Cu^2+/1+ redox potential range of 1.3 V. We have found that the redox potential influenced the Faradaic efficiency of CO₂ reduction to CO. However, no correlation between the redox potential and the Faradaic efficiency for methane was found. The lack of correlation could be attributed to the presence of a Cu-complex-derived catalyst deposited on the electrodes leading to a heterogeneous catalytic mechanism, which is controlled by the structure of the in situ deposited catalyst and not the redox potential of the pre-cursor Cu^2+/1+ complexes. Full article

A series of nine cationic heteroleptic aryl-BIAN-copper(I) (BIAN = bis-iminoacenaphthene) complexes with the general formula [Cu((E-C₆H₄)₂BIAN)(PPh₃)₂][X] (E = p-Me, p-iPr, o-iPr; X = BF₄, OTf, NO₃) 1^X–3^X were synthesized and fully characterized using several analytical techniques, including NMR spectroscopy and single-crystal X-ray diffraction. Except for complexes 2^BF₄ and 3^BF₄, which were already reported in our previous works, all remaining complexes are herein described for the first time. Two different strategies were used for the preparation of the complexes: complexes bearing BF₄⁻ or OTf⁻ counter-ions (1^BF₄, 1^OTf, 2^OTf, and 3^OTf) were obtained using the appropriate copper(I) precursors [Cu(NCMe)₄][BF₄] or [Cu(NCMe)₄][OTf], whereas for derivatives 1^NO₃–3^NO₃, [Cu(PPh₃)₂NO₃] was used. Their activity as catalysts for the copper azide-alkyne cycloaddition (CuAAC) was assessed alongside other high activity, previously reported Cu(I) complexes. Comparative studies to determine the influence of the counter-ion and of the aryl substituents were performed. All complexes behaved as active catalysts under neat reaction conditions, at 25 °C and in short reaction times without requiring the use of any additive, with complex 2^NO₃ being the most efficient derivative, along with other NO₃⁻-bearing complexes. Full article

Extraordinary low-temperature vapor-phase synthesis of SnS thin films from single molecular precursors is attractive over conventional high-temperature solid-state methods. Molecular-level processing of functional materials is accompanied by several intrinsic advantages such as precise control over stoichiometry, phase selective synthesis, and uniform substrate coverage. We report here on the synthesis of a new heteroleptic molecular precursor containing (i) a thiolate ligand forming a direct Sn-S bond, and (ii) a chelating O^N^N-donor ligand introducing a “launch vehicle”-effect into the synthesized compound, thus remarkably increasing its volatility. The newly synthesized tin compound [Sn(SBu^t)(tfb-dmeda)] 1 was characterized by single-crystal X-ray diffraction analysis that verified the desired Sn:S ratio in the molecule, which was demonstrated in the direct conversion of the molecular complex into SnS thin films. The multi-nuclei (¹H, ¹³C, ¹⁹F, and ¹¹⁹Sn) and variable-temperature 1D and 2D NMR studies indicate retention of the overall solid-state structure of 1 in the solution and suggest the presence of a dynamic conformational equilibrium. The fragmentation behavior of 1 was analyzed by mass spectrometry and compared with those of homoleptic tin tertiary butyl thiolates [Sn(SBu^t)₂] and [Sn(SBu^t)₄]. The precursor 1 was then used to deposit SnS thin films on different substrates (FTO, Mo-coated soda-lime glass) by CVD and film growth rates at different temperatures (300–450 °C) and times (15–60 min), film thickness, crystalline quality, and surface morphology were investigated. Full article

A set of heteroleptic ethyl zinc $\beta$-amidoenoates (1, 2) and $\beta$-ketoiminates (3) of the form [LZnEt]₂ with varying steric bulk have been synthesised via the reaction of diethylzinc with $\beta$-aminoenoate ligands HL¹ and HL² and $\beta$-ketoimine HL³. These complexes have been characterised via ¹H and ¹³C NMR, mass spectrometry and single-crystal X-ray diffraction, which unambiguously determined all three structures as dimeric species in the solid state. We observe the unusual dimerisation of 1 and 2 through coordination of the central zinc atom to the methine carbon of the second monomer, which gives these complexes high reactivity. The thermal properties of complex 3 are explored via thermal gravimetric analysis (TGA), to investigate their potential as single-source precursors to zinc oxide, which shows that 3 has a significantly lower decomposition temperature as compared to its bis-ligated counterpart [Zn(L³)₂], which gives 3 promise as a single-source precursor to zinc oxide. Full article

The thermal atomic layer deposition (ThALD) of yttrium oxide (Y₂O₃) was developed using the newly designed, liquid precursor, Y(EtCp)₂(ⁱPr₂-amd), as the yttrium source in combination with different oxygen sources, such as ozone, water and even molecular oxygen. Saturation was observed for the growth of the Y₂O₃ films within an ALD window of 300 to 450 °C and a growth per cycle (GPC) up to 1.1 Å. The resulting Y₂O₃ films possess a smooth and crystalline structure, while avoiding any carbon and nitrogen contamination, as observed by X-ray photoelectron spectroscopy (XPS). The films showed strong resistance to fluorine-containing plasma, outperforming other resistant materials, such as silicon oxide, silicon nitride and alumina. Interestingly, the hydrophilic character exhibited by the film could be switched to hydrophobic after exposure to air, with water contact angles exceeding 90°. After annealing under N₂ flow at 600 °C for 4 min, the hydrophobicity was lost, but proved recoverable after prolonged air exposure or intentional hydrocarbon exposure. The origin of these changes in hydrophobicity was examined. Full article

A robust sol-gel process was developed for the synthesis of surface-functionalized titania nanocrystallites bearing unsaturated groups starting from molecular heteroleptic single-source precursors. Molecules and nanomaterials were thoroughly characterized by multinuclear liquid and solid-state nuclear magnetic resonance (NMR), infra-red (FT-IR, DRIFT) spectroscopies. Nitrogen adsorption-desorption (BET), thermogravimetric (TG) and elemental analyses demonstrated the reliability and the fine tuning of the surface functionalization in terms of ratio TiO₂:ligand. The as-prepared materials were used as nano-adsorbents to remove mixture of 16 polycyclic aromatic hydrocarbon (PAHs) from aqueous solutions. Adsorption kinetic experiments were carried out for 24 h in solutions of one PAH [benzo(a)pyrene, 220 ppb] and of a mixture of sixteen ones [220 ppb for each PAH]. Most kinetic data best fitted the pseudo-second order model. However, in PAHs mixture, a competition process took place during the first hours leading to a remarkable high selectivity between light and heavy PAHs. This selectivity could be fine-tuned depending on the nature of the unsaturated group of the phosphonate framework and on the nanomaterial textures. Full article