Steady state emission spectra and excited state lifetimes were measured for 1440 distinct heteroleptic [Ir(C^N)2(N^N)]+ complexes prepared via combinatorial parallelized synthesis; 72% of the complexes were found to be luminescent, and the emission maxima of the library spanned the visible spectrum (652–459 nm). Spectral profiles ranged from broad structureless bands to narrow emissions exhibiting vibrational substructure. Measured excited state lifetimes ranged between ∼0.1–14 μs. Automated emission spectral fitting with successive Gaussian functions revealed four distinct measured classes of excited states; in addition to well understood metal–ligand to ligand-charge transfer (3MLLCT) and ligand-centered (3LC) excited states, our classification also identified photophysical characteristics of less explored mixed 3MLLCT/3LC states. Electronic structure features obtained from DFT calculations performed on a large subset of these Ir(III) chromophores offered clear insights into the excited state properties and allowed the prediction of structure/luminescence relationships in this class of commonly used photocatalysts. Models with high prediction accuracy (R2 = 0.89) for emission color were developed on the basis of experimental data. Furthermore, different degrees of nuclear reorganization in the excited state were shown to significantly impact emission energy and excited state lifetimes.
A high-throughput optical screening method for the photocatalytic activity of a structurally diverse library of 1152 cationic iridium(III) complexes ([Ir(C^N)2(N^N)]+), corresponding to all combinations of 48 cyclometalating (C^N) and 24 ancillary (N^N) ligands, was developed. This rapid assay utilizes the colorimetric changes of a high contrast indicator dye, coumarin 6, to monitor the photo-induced electron transfer from a sacrificial amine donor to the metal complex excited state. The resulting [Ir(C^N)2(N^N)]0 can then reduce an aryl bromide to form the highly reactive aryl radical intermediate. The rate of this reaction is dictated by the molecular structure of both coordinating ligands. Relative reaction rate constants determined via this method correlated closely with 19F NMR measurements obtained using a fluorinated substrate. A simple model that expresses the rate constant as a product of a single ″strength″ parameter assigned to each of the 72 ligands can well account for the 1152 measured rate constants. The best performing complexes exhibit much higher reactivity than the benchmark photocatalysts commonly used in photoredox transformations. The catalysts were also successfully tested for their chemoselectivity. The developed screening methodology can enable generation of the large data sets needed to use modern data science to extract structure–activity relationships.
High-throughput synthesis and screening methods were used to measure the photochemical activity of 1440 distinct heteroleptic [Ir(C^N) 2 (N^N)] + complexes for the photoreduction of Sn(II) and Zn(II) cations to their corresponding neutral metals. Kinetic data collection was carried out using home-built photoreactors and measured initial rates, obtained through an automated fitting algorithm, spanned between 0−120 μM/s for Sn(0) deposition and 0−90 μM/s for Zn(0) deposition. Photochemical reactivity was compared to photophysical properties previously measured such as deaerated excited state lifetime and emission spectral data for these same complexes; however, no clear correlations among these features were observed. A formal photochemical rate law was then developed to help elucidate the observed reactivity. Initial rates were found to be directly correlated to the product of incident photon flux with three reaction elementary efficiencies: (1) the fraction of light absorbed by the photocatalyst, (2) the fraction of excited state species that are quenched by the electron donor, and (3) the cage escape efficiency. The most active catalysts exhibit high efficiencies for all three steps, and catalyst engineering requirements to maximize these elementary efficiencies were postulated. The kinetic treatment provided the mechanistic information needed to decipher the observed structure/function trends in the high-throughput work.
Based on previous work that identified iridium(III) Cp* complexes containing a C,N‐bidentate chelating triazolylidene‐pyridyl ligand (Cp* = pentamethylcyclopentadienyl, C5Me5–) as efficient molecular water oxidation catalysts, a series of new complexes based on this motif has been designed and synthesized in order to improve catalytic activity. Modifications include specifically the introduction of electron‐donating substituents into the pyridyl unit of the chelating ligand (H, a; 5‐OMe, b; 4‐OMe, c; 4‐tBu, d; 4‐NMe2, e), as well as electronically active substituents on the triazolylidene C4 position (H, 8; COOEt, 9; OEt, 10; OH, 11; COOH, 12). Chemical oxidation using cerium ammonium nitrate (CAN) indicates a clear structure‐activity relationship with electron‐donating groups enhancing catalytic turnover frequency, especially when the donor substituent is positioned on the triazolylidene ligand fragment (TOFmax = 2500 h–1 for complex 10 with a MeO group on pyr and a OEt‐substituted triazolylidene, compared to 700 h–1 for the parent benchmark complex without substituents). Electrochemical water oxidation does not follow the same trend, and reveals that complex 8b without a substituent on the triazolylidene fragment outperforms complex 10 by a factor of 5, while in CAN‐mediated chemical water oxidation, complex 10 is twice more active than 8b. This discrepancy in catalytic activity is remarkable and indicates that caution is needed when benchmarking iridium water oxidation catalysts with chemical oxidants, especially when considering that application in a potential device will most likely involve electrocatalytic water oxidation.
The heptadentate ligand, tris-(2-(2-(methylthio)phenylamino)ethyl)amine (2), has been synthesized from the condensation of nitrilotriacetyl chloride with 2-(methylthio)aniline, to generate 2,2',2"-nitrilotris(N-(2-(methylthio)phenyl)acetamide) (1), followed by a lithium aluminum hydride reduction. The zirconium (3) and hafnium (4) complexes of this ligand were generated via transamination reactions. Both complexes are isostructural, exhibiting a hexadentate N 4 S 2 coordination from the ligand, with one diethylamido ligand also bound. The solid state structures of all compounds are reported.
Iminophosphorane P(V) compounds are accessed via electrochemical oxidation of commercially available P(III) ligands, including mono-, di- and tri-dentate phosphines as well as chiral phosphines. The reaction uses inexpensive bis(trimethylsilyl)carbodiimide as an efficient and safe aminating reagent. DFT calculations, cyclic voltammetry, and NMR spectroscopic studies provide insight into the reaction mechanism. The proposed mechanism based on the data reveals a special case of sequential paired electrolysis, namely a domino electrolysis process in which intermediates generated at the cathode are subsequently oxidized at the anode, followed by an additional convergent paired electrolysis process. DFT calculations of the frontier orbitals of the iminophosphorane are compared to those of the analogous P(III) phosphines and P(V) phosphine oxides. This reveals that N-cyano-iminophosphoranes have both a higher HOMO and lower LUMO than their analogous phosphine oxide, rendering them suitable for both sigma-donating and pi-back-bonding.
A modular synthesis of tris(aryl)tren ligands has been demonstrated via the condensation of nitrilotracetyl chloride with different anilines followed by reduction. Varying the aniline in the condensation step from 2-methylthioaniline, to 2-phenylthioaniline, to 2-chloroaniline, generates 2,2',2"-nitrilotris(N-(2-(methylthio)phenyl)acetamide (1), 2,2',2"-nitrilotris(N-(2-(phenylthio)phenyl)acetamide (2) and 2,2',2"-nitrilotris(N-2-chlorophenyl)acetamide (3) respectively. The 2-chloroaniline synthesis is complicated by the production of N-(2chlorophenyl)-3,5-dioxo-1-piperazine-N-(2-chlorophenyl)acetamide (4), but can be adjusted to produce only 3. The reduction of complexes 1-3 proceeds with lithium aluminum hydride for 1 and 2 and with borane for 3 to yield the tris(aryl)tren ligands tris-(2-(2-(methylthio)phenylamino)ethyl)amine (5), tris-(2-(2-(phenylthio)phenylamino)ethyl)amine (6), and tris-(2-(2-chlorophenylamino)ethyl)amine (7). All three of these ligands can be deprotonated with tert-butyllithium for 5 and 7, and n-butyllithium for 6 to generate their trilithium complexes, 8, 9 and 10 for 5, 6 and 7 respectively, with 10 forming two different solvates (10a and 10b). All complexes are characterized by 1 H and 13 C NMR and the solid state structures of complexes 2, 3, 4, 7, 8, 9, 10a and 10b are described.
This work describes a photocatalytic process using the oxidation of biorenewable alcohols as the electron/proton source for the photogeneration of hydrogen. The approach utilizes a molecular iridium photosensitizer (PS), an in situ synthesized Pd-containing colloid catalyst, and a redox shuttle (RS). By virtue of the high-throughput photoreactor utilized in this work, rapid reaction parameter screening for five donor species (oxalic acid, benzyl alcohol, isopropanol, ethanol, and glycerol) was undertaken, resulting in the identification of reaction conditions conducive to the formation of hydrogen from all species. Using these newly identified reaction conditions, screening was undertaken for 96 uniquely structured iridium organometallic complexes as photocatalysts and for a set of structurally diverse RSs. The top-performing PS resulted in catalytic turnover numbers (TONs) of 81 for glycerol (quantum yield (Φ) = 0.73%), 100 for isopropanol (Φ = 1.21%), 133 for ethanol (Φ = 0.91%), and 159 for oxalic acid (Φ = 1.44%). The wealth of data on the inner workings of these light-driven alcohol-reforming reactions was supplemented with nanoparticle characterization of select candidates by transmission electron microscopy and X-ray photoelectron spectroscopy, and identification and quantification of the alcohols' oxidation products was undertaken via 1 H NMR.
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