Exploiting Organometallic Chemistry to Functionalize Small Cuprous Oxide Colloidal Nanocrystals.

The ligand chemistry of colloidal semiconductor nanocrystals mediates their solubility, band gap, and surface facets. Here, selective organometallic chemistry is used to prepare small, colloidal cuprous oxide nanocrystals and to control their surface chemistry by decorating them with metal complexes. The strategy is demonstrated using small (3-6 nm) cuprous oxide (Cu2O) colloidal nanocrystals (NC), soluble in organic solvents. Organometallic complexes are coordinated by reacting the surface Cu-OH bonds with organometallic reagents, M(C6F5)2, M = Zn(II) and Co(II), at room temperature. These reactions do not disrupt the Cu2O crystallinity or nanoparticle size; rather, they allow for the selective coordination of a specific metal complex at the surface. Subsequently, the surface-coordinated organometallic complex is reacted with three different carboxylic acids to deliver Cu-O-Zn(O2CR') complexes. Selective nanocrystal surface functionalization is established using spectroscopy (IR, 19F NMR), thermal gravimetric analyses (TGA), transmission electron microscopy (TEM, EELS), and X-ray photoelectron spectroscopy (XPS). Photoluminescence efficiency increases dramatically upon organometallic surface functionalization relative to that of the parent Cu2O NC, with the effect being most pronounced for Zn(II) decoration. The nanocrystal surfaces are selectively functionalized by both organic ligands and well-defined organometallic complexes; this synthetic strategy may be applicable to many other metal oxides, hydroxides, and semiconductors. In the future, it should allow NC properties to be designed for applications including catalysis, sensing, electronics, and quantum technologies.

Hydrobismuthation: Insertion of Unsaturated Hydrocarbons into the Heaviest Main Group Element Bond to Hydrogen.

The bismuth hydride (2,6-Mes2H3C6)2BiH (1, Mes = 2,4,6-trimethylphenyl), which has a Bi-H 1H NMR spectroscopic signal at δ = 19.64 ppm, was reacted with phenylacetylene at 60 °C in toluene to yield [(2,6-Mes2C6H3)2BiC(Ph)=CH2] (2) after 15 min. Compound 2 was characterized by 1H, 13C NMR, and UV-vis spectroscopy, single crystal X-ray crystallography, and calculations employing density functional theory. Compound 2 is the first example of a hydrobismuthation addition product and displays Markovnikov regioselectivity. Computational methods indicated that it forms via a radical mechanism with an associated Gibbs energy of activation of 91 kJ mol-1 and a reaction energy of -90 kJ mol-1.

Sn(II)-carbon bond reactivity: radical generation and consumption via reactions of a stannylene with alkynes.

Thermal Sn-C cleavage in the diarylstannylene Sn(AriPr4)2 (AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2) was used to generate ˙Sn(AriPr4) and ˙AriPr4 radicals for alkyne arylstannylation. The radical pair and RCCR' (R = H, R' = Ph; R = Ph, R' = Ph; R = H, R' = C4H9; R = H, R' = SiMe3) in refluxing benzene generate the aryl vinyl stannylene complexes, AriPr4Sn{C(C6H5)-C(H)(AriPr4)} (1), AriPr4Sn{C(C6H5)-C(H)(C6H5)} (2) and AriPr4Sn{C(C4H9)-C(H)(AriPr4)} (3) respectively. For HCCSiMe3, the known distannene {Sn(CCSiMe3)AriPr4}2 (4) was also generated from this new method.

London Dispersion Effects on the Stability of Heavy Tetrel Molecules.

London dispersion (LD) interactions, which stem from long-range electron correlations arising from instantaneously induced dipoles can occur between neighboring atoms or molecules, for example, between H atoms within ligand C-H groups. These interactions are currently of interest as a new method of stabilizing long bonds and species with unusual oxidation states. They can also limit reactivity by installing LD enhanced groups into organic frameworks or ligand substituents. Here, we address the most recent advances in the design of LD enhanced ligands, the sterically counterintuitive structures that can be generated and the consequences that these interactions can have on the structures and reactivity of sterically crowded heavy group 14 species.

Disproportionation of Sn(II){CH(SiMe3)2}2 to ˙Sn(III){CH(SiMe3)2}3 and ˙Sn(I){CH(SiMe3)2}: characterization of the Sn(I) product.

Half a century after the photolytic disproportionation of Lappert's dialkyl stannylene SnR2, R = CH(SiMe3)2 (1) gave the persistent trivalent radical [˙SnR3], the characterization of the corresponding Sn(I) product, ˙SnR is now described. It was isolated as the hexastannaprismane Sn6R6 (2), from the reduction of 1 by the Mg(I)-reagent, Mg(BDIDip)2 (BDI = (DipNCMe)2CH, Dip = 2,6-diisopropylphenyl).

London Dispersion Effects in a Distannene/Tristannane Equilibrium: Energies of their Interconversion and the Suppression of the Monomeric Stannylene Intermediate.

Reaction of {LiC6 H2 -2,4,6-Cyp3 ⋅Et2 O}2 (Cyp=cyclopentyl) (1) of the new dispersion energy donor (DED) ligand, 2,4,6-triscyclopentylphenyl with SnCl2 afforded a mixture of the distannene {Sn(C6 H2 -2,4,6-Cyp3 )2 }2 (2), and the cyclotristannane {Sn(C6 H2 -2,4,6-Cyp3 )2 }3 (3). 2 is favored in solution at higher temperature (345 K or above) whereas 3 is preferred near 298 K. Van't Hoff analysis revealed the 3 to 2 conversion has a ΔH=33.36 kcal mol-1 and ΔS=0.102 kcal mol-1 K-1 , which gives a ΔG300 K =+2.86 kcal mol-1 , showing that the conversion of 3 to 2 is an endergonic process. Computational studies show that DED stabilization in 3 is -28.5 kcal mol-1 per {Sn(C6 H2 -2,4,6-Cyp3 )2 unit, which exceeds the DED energy in 2 of -16.3 kcal mol-1 per unit. The data clearly show that dispersion interactions are the main arbiter of the 3 to 2 equilibrium. Both 2 and 3 possess large dispersion stabilization energies which suppress monomer dissociation (supported by EDA results).

Unraveling the Steric Link to Copper Precursor Decomposition: A Multi-Faceted Study for the Printing of Flexible Electronics.

The field of printed electronics strives for lower processing temperatures to move toward flexible substrates that have vast potential: from wearable medical devices to animal tagging. Typically, ink formulations are optimized using mass screening and elimination of failures; as such, there are no comprehensive studies on the fundamental chemistry at play. Herein, findings which describe the steric link to decomposition profile: combining density functional theory, crystallography, thermal decomposition, mass spectrometry, and inkjet printing, are reported. Through the reaction of copper(II) formate with excess alkanolamines of varying steric bulk, tris-co-ordinated copper precursor ions: "[CuL3 ]," each with a formate counter-ion (1-3) are isolated and their thermal decomposition mass spectrometry profiles are collected to assess their suitability for use in inks (I1-3 ). Spin coating and inkjet printing of I1,2 provides an easily up-scalable method toward the deposition of highly conductive copper device interconnects (ρ = 4.7-5.3 × 10-7 Ω m; ≈30% bulk) onto paper and polyimide substrates and forms functioning circuits that can power light-emitting diodes. The connection among ligand bulk, coordination number, and improved decomposition profile supports fundamental understanding which will direct future design.

Terpene dispersion energy donor ligands in borane complexes.

Structural characterization of the complex [B(ß-pinane)3] (1) reveals non-covalent H⋯H contacts that are consistent with the generation of London dispersion energies involving the ß-pinane ligand frameworks. The homolytic fragmentations of 1, and camphane and sabinane analogues ([B(camphane)3] (2) and [B(sabinane)3] (3)) were studied computationally. Isodesmic exchange results showed that London dispersion interactions are highly dependent on the terpene's stereochemistry, with the ß-pinane framework providing the greatest dispersion free energy (ΔG = -7.9 kcal mol-1) with Grimme's dispersion correction (D3BJ) employed. PMe3 was used to coordinate to [B(ß-pinane)3], giving the complex [Me3P-B(ß-pinane)3] (4), which displayed a dynamic coordination equilibrium in solution. The association process was found to be slightly endergonic at 302 K (ΔG = +0.29 kcal mol-1).

Beyond Steric Crowding: Dispersion Energy Donor Effects in Large Hydrocarbon Ligands.

Interactions between sterically crowded hydrocarbon-substituted ligands are widely considered to be repulsive because of the intrusion of the electron clouds of the ligand atoms into each other's space, which results in Pauli repulsion. Nonetheless, there is another interaction between the ligands which is less widely publicized but is always present. This is the London dispersion (LD) interaction which can occur between atoms or molecules in which dipoles can be induced instantaneously, for example, between the H atoms from the ligand C-H groups.These LD interactions are always attractive, but their effects are not as widely recognized as those of the Pauli repulsion despite their central role in the formation of condensed matter. Their relatively poor recognition is probably due to the relative weakness (ca. 1 kcal mol-1) of individual H···H interactions owing to their especially strong distance dependence. In contrast, where there are numerous H···H interactions, a collective LD energy equaling several tens of kcal mol-1 may ensue. As a result, in some molecules the latent importance of the LD attraction energies emerges and assumes a prominence that can overshadow the Pauli effects (e.g., in the stabilization of high-oxidation-state transition-metal alkyls, inducing disproportionation reactions, or in the stabilization of otherwise unstable bonds).Despite being known for over a century, the accurate quantification of individual H···H LD effects in molecular species is a relatively recent phenomenon and at present is based mainly on modified DFT calculations. A few leading reviews summarized these earlier studies of the C-H···H-C LD interactions in organic molecules, and their effects on the structures and stabilities were described. LD effects in sterically crowded inorganic and organometallic molecules have been recognized.The author's interest in these LD effects arose fortuitously over a decade ago during research on sterically crowded heavier main-group element carbene analogues and two-coordinate, open-shell (d1-d9) transition-metal complexes where counterintuitive steric effects were observed. More detailed explanations of these effects were provided by dispersion-corrected DFT calculations in collaboration with the groups of Tuononen and Nagase (see below).This Account describes our development of these initial results for other inorganic molecular classes. More recently, the work has led us to move to the planned inclusion of dispersion effects in ligands to stabilize new molecular types with theoretical input from the groups of Vasko and Grimme (see below). Our approach sought to use what Grimme has described as dispersion effect donor (DED) groups (i.e., spatially close-lying, densely packed substituents either as ligands (e.g., -C6H2-2,4,6-Cy3, Cy = cyclohexyl) or as parts of ligands (e.g., a Cy substituent) that produce relatively large dispersion energies to stabilize these new compounds.We predict that the future design of sterically crowding hydrocarbon ligands will include the consideration and incorporation of LD effects as a standard methodology for directed use in the attainment of new synthetic targets.

Inhibition of Alkali Metal Reduction of 1-Adamantanol by London Dispersion Effects.

A series of alkali metal 1-adamantoxide (OAd1 ) complexes of formula [M(OAd1 )(HOAd1 )2 ], where M=Li, Na or K, were synthesised by reduction of 1-adamantanol with excess of the alkali metal. The syntheses indicated that only one out of every three HOAd1 molecules was reduced. An X-ray diffraction study of the sodium derivative shows that the complex features two unreduced HOAd1 donors as well as the reduced alkoxide (OAd1 ), with the Ad1 fragments clustered together on the same side of the NaO3 plane, contrary to steric considerations. This is the first example of an alkali metal reduction of an alcohol that is inhibited from completion due to the formation of the [M(OAd1 )(HOAd1 )2 ] complexes, stabilized by London dispersion effects. NMR spectroscopic studies revealed similar structures for the lithium and potassium derivatives. Computational analyses indicate that decisive London dispersion effects in the molecular structure are a consequence of the many C-H⋅⋅⋅H-C interactions between the OAd1 groups.

Investigations into the structure, reactivity, and AACVD of aluminium and gallium amidoenoate complexes.

Amidoenoate (AME = {ethyl-3-(R-amido)but-2-enoate}) complexes of aluminium and gallium, of the type: [AlCl2(AMER)] R = iPr (1-Al); [AlCl(AMER)2] R = iPr (2-Al), Dip (3-Al); [GaCl2(AMER)] R = iPr (1-Ga) and [GaCl(AMER)2] R = iPr (2-Ga), Dip (3-Ga), have been synthesised (iPr = isopropyl, Dip = 2,6-diisopropylphenyl). The coordination chemistry of these complexes has been studied in relation to precursor suitability. Investigations into the reactivity of the aluminium and gallium amidoenoate complexes involved reactions with hydride sources including alkali metal hydride salts, alkylsilanes, and magnesium hydride species and magnesium(I) dimers. The isolation of alkyl metal amidoenoate precursors including an aluminium hydride amidoenoate, [AlH(AMEDip)2] (4-Al) and dimethyl gallium amidoenoates [GaMe2(AMEDip)] (4-Ga), [GaMe2(AMEiPr)] (5-Ga) concluded the synthetic studies. A selection of the isolated complexes were used as precursors for aerosol assisted chemical vapour deposition (AACVD) at 500 °C. Thin films of either amorphous Al2O3 or Ga2O3 were deposited and subsequently annealed at 1000 °C to improve the materials' crystallinity. The films were characterised by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV-visible (UV-vis) spectroscopy and energy dispersive X-ray analysis (EDXA).

Synthesis, solution dynamics and chemical vapour deposition of heteroleptic zinc complexes via ethyl and amide zinc thioureides.

Ethyl and amide zinc thioureides [L1ZnEt]2 (1), [L1*ZnEt]2 (2) and [L1Zn(N(SiMe3)2)]2 (3) have been synthesised from the equimolar reaction of thiourea ligands (HL1 = iPrN(H)CSNMe2 and HL1* = PhN(H)CSNMe2) with diethyl zinc and zinc bis[bis(trimethylsilyl)amide] respectively. New routes towards heteroleptic complexes have been investigated through reactions of 1, 2 and 3 with ß-ketoiminates (HL2 = [(Me)CN(H){iPr}-CHC(Me)[double bond, length as m-dash]O]), bulky aryl substituted ß-diiminates (HL3 = [(Me)CN(H){Dipp}-CHC(Me)[double bond, length as m-dash]N{Dipp}] (Dipp = diisopropylphenyl) and HL3* = [(Me)CN(H){Dep}-CHC(Me)[double bond, length as m-dash]N{Dep}] (Dep = diethylphenyl)) and donor-functionalised alcohols (HL4 = Et2N(CH2)3OH and HL4* = Me2N(CH2)3OH) and have led to the formation of the heteroleptic complexes [L1*ZnL3*] (5), [L1ZnL4]2 (6), [L1ZnL4*]2 (7), [L1*ZnL4] (8) and [L1*ZnL4*] (9). All complexes have been characterised by 1H and 13C NMR, elemental analysis, and the X-ray structures of HL1*, 1, 2, 6 and 7 have been determined via single crystal X-ray diffraction. Variable temperature 1H, COSY and NOESY NMR experiments investigating the dynamic behaviour of 5, 6 and 7 have shown these molecules to be fluxional. On the basis of solution state fluxionality and thermogravimetric analysis (TGA), alkoxyzinc thioureides 6 and 7 were investigated as single-source precursors for the deposition of the ternary material zinc oxysulfide, Zn(O,S), a buffer layer used in thin film photovoltaic devices. The aerosol-assisted chemical vapour deposition (AACVD) reaction of 7 at 400 °C led to the deposition of the heterodichalcogenide material Zn(O,S), which was confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDX), with optical properties investigated using UV/vis spectroscopy, and surface morphology and film thickness examined using scanning electron microscopy (SEM).

Molecular Complexes Featuring Unsupported Dispersion-Enhanced Aluminum-Copper and Gallium-Copper Bonds.

The reaction of the copper(I) ß-diketiminate copper complex {(Cu(BDIMes))2(µ-C6H6)} (BDIMes = N,N'-bis(2,4,6-trimethylphenyl)pentane-2,4-diiminate) with the low-valent group 13 metal ß-diketiminates M(BDIDip) (M = Al or Ga; BDIDip = N,N'-bis(2,6-diisopropylphenyl)pentane-2,4-diiminate) in toluene afforded the complexes {(BDIMes)CuAl(BDIDip)} and {(BDIMes)CuGa(BDIDip)}. These feature unsupported copper-aluminum or copper-gallium bonds with short metal-metal distances, Cu-Al = 2.3010(6) Å and Cu-Ga = 2.2916(5) Å. Density functional theory (DFT) calculations showed that approximately half of the calculated association enthalpies can be attributed to London dispersion forces.

Structural and Dynamic Properties of Gallium Alkoxides.

A comparison of chlorido-gallium functionalized alkoxides as precursors for aerosol-assisted chemical vapor deposition (AACVD) was carried out. Variable-temperature (VT)-NMR studies were used to probe the fluxional behavior of these alkoxides in solution, and hence their utility as precursors. The synthesis involved the initial isolation of the dimer [GaCl(NMe2)2]2 via a salt metathesis route from GaCl3 and 2 equiv of LiNMe2. This dimer was then reacted with 4 equiv of HOCH2CH2CH2NEt2, resulting in the formation of Ga[µ-(OCH2CH2CH2NEt2)2GaCl2]3 (1). Mass spectrometry and VT-NMR confirmed the oligomeric structure of 1. Tuning of the ligand properties, namely, the chain length and substituents on N, resulted in formation of the monomers [GaCl(OR)2] (R = CH2CH2NEt2, (2); CH2CH2CH2NMe2, (3)). VT-NMR studies, supported by density functional theory calculations, confirmed that the ligands in both 2 and 3 possess a hemilabile coordination to the gallium center, owing to either a shorter carbon backbone (2) or less steric hindrance (3). Both 2 and 3 were selected for use as precursors for AACVD: deposition at 450 °C gave thin films of amorphous Ga2O3, which were subsequently annealed at 1000 °C to afford crystalline Ga2O3 material. The films were fully characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, UV-visible spectroscopy, and energy dispersive X-ray analysis.