Color morphing surfaces with effective chemical shielding.

Color morphing refers to color change in response to an environmental stimulus. Photochromic materials allow color morphing in response to light, but almost all photochromic materials suffer from degradation when exposed to moist/humid environments or harsh chemical environments. One way of overcoming this challenge is by imparting chemical shielding to the color morphing materials via superomniphobicity. However, simultaneously imparting color morphing and superomniphobicity, both surface properties, requires a rational design. In this work, we systematically design color morphing surfaces with superomniphobicity through an appropriate combination of a photochromic dye, a low surface energy material, and a polymer in a suitable solvent (for one-pot synthesis), applied through spray coating (for the desired texture). We also investigate the influence of polymer polarity and material composition on color morphing kinetics and superomniphobicity. Our color morphing surfaces with effective chemical shielding can be designed with a wide variety of photochromic and thermochromic pigments and applied on a wide variety of substrates. We envision that such surfaces will have a wide range of applications including camouflage soldier fabrics/apparel for chem-bio warfare, color morphing soft robots, rewritable color patterns, optical data storage, and ophthalmic sun screening.

Deciphering Charge Transfer Processes in Transition Metal Complexes from the Perspective of Ultrafast Electronic and Nuclear Motions.

Chemical transformations in charge transfer states result from the interplay between electronic dynamics and nuclear reorganization along excited-state trajectories. Here, we investigate the ultrafast structural dynamics following photoinduced electron transfer from the metal-metal-to-ligand charge transfer state of an electron donor, a Pt dimer complex, to a covalently linked electron acceptor group using ultrafast time-resolved wide-angle X-ray scattering and optical transient absorption spectroscopy methods to disentangle the interdependence of the excited-state electronic and nuclear dynamics. Following photoexcitation, Pt-Pt bond formation and contraction takes up to 1 ps, much slower than the corresponding process in analogous complexes without electron acceptor groups. Because the Pt-Pt distance change is slow with respect to excited-state electron transfer, it can affect the rate of electron transfer. These results have potential impacts on controlling electron transfer rates via structural alterations to the electron donor group, tuning the charge transfer driving force.

Enhanced Visible Light Absorption in Heteroleptic Cuprous Phenanthrolines.

This work presents a series of Cu(I) heteroleptic 1,10-phenanthroline chromophores featuring enhanced UVA and visible-light-harvesting properties manifested through vectorial control of the copper-to-phenanthroline charge-transfer transitions. The molecules were prepared using the HETPHEN strategy, wherein a sterically congested 2,9-dimesityl-1,10-phenanthrolne (mesPhen) ligand was paired with a second phenanthroline ligand incorporating extended π-systems in their 4,7-positions. The combination of electrochemistry, static and time-resolved electronic spectroscopy, 77 K photoluminescence spectra, and time-dependent density functional theory calculations corroborated all of the experimental findings. The model chromophore, [Cu(mesPhen)(phen)]+ (1), lacking 4,7-substitutions preferentially reduces the mesPhen ligand in the lowest energy metal-to-ligand charge-transfer (MLCT) excited state. The remaining cuprous phenanthrolines (2-4) preferentially reduce their π-conjugated ligands in the low-lying MLCT excited state. The absorption cross sections of 2-4 were enhanced (εMLCTmax = 7430-9980 M-1 cm-1) and significantly broadened across the UVA and visible regions of the spectrum compared to 1 (εMLCTmax = 6494 M-1 cm-1). The excited-state decay mechanism mirrored those of long-lived homoleptic Cu(I) phenanthrolines, yielding three distinguishable time constants in ultrafast transient absorption experiments. These represent pseudo-Jahn-Teller distortion (τ1), singlet-triplet intersystem crossing (τ2), and the relaxed MLCT excited-state lifetime (τ3). Effective light-harvesting from Cu(I)-based chromophores can now be rationalized within the HETPHEN strategy while achieving directionality in their respective MLCT transitions, valuable for integration into more complex donor-acceptor architectures and longer-lived photosensitizers.

Sterically Encumbered Heteroleptic Copper(I) ß-Diketiminate Complexes with Extended Excited-State Lifetimes.

One of the main challenges in developing effective copper(I) photosensitizers is their short excited-state lifetimes, usually attributed to structural distortion upon light excitation. We have previously introduced copper(I) charge-transfer chromophores of the general formula Cu(N^N)(ArNacNac), where N^N is a conjugated diimine ligand and ArNacNac is a substituted ß-diketiminate ligand. These chromophores were promising regarding their tunable redox potentials and intense visible absorption but were ineffective as photosensitizers, presumably due to short excited-state lifetimes. Here, we introduce sterically crowded analogues of these heteroleptic chromophores with bulky alkyl substituents on the N^N and/or ArNacNac ligand. Structural analysis was combined with electrochemical and photophysical characterization, including ultrafast transient absorption (UFTA) spectroscopy to investigate the effects of the alkyl groups on the excited-state lifetimes of the complexes. The molecular structures determined by single-crystal X-ray diffraction display more distortion in the ground state as alkyl substituents are introduced into the phenanthroline or the NacNac ligand, showing smaller τ4 values due to the steric hindrance. UFTA measurements were carried out to determine the excited-state dynamics. Sterically encumbered Cu5 and Cu6 display excited-state lifetimes 15-20 times longer than unsubstituted complex Cu1, likely indicating that the incorporation of bulky alkyl substituents inhibits the pseudo-Jahn-Teller (PJT) flattening distortion in the excited state. This work suggests that the steric properties of these heteroleptic copper(I) charge-transfer chromophores can be readily modified and that the excited-state dynamics are strongly responsive to these modifications.

Spin-vibronic coherence drives singlet-triplet conversion.

Design-specific control over the transitions between excited electronic states with different spin multiplicities is of the utmost importance in molecular and materials chemistry1-3. Previous studies have indicated that the combination of spin-orbit and vibronic effects, collectively termed the spin-vibronic effect, can accelerate quantum-mechanically forbidden transitions at non-adiabatic crossings4,5. However, it has been difficult to identify precise experimental manifestations of the spin-vibronic mechanism. Here we present coherence spectroscopy experiments that reveal the interplay between the spin, electronic and vibrational degrees of freedom that drive efficient singlet-triplet conversion in four structurally related dinuclear Pt(II) metal-metal-to-ligand charge-transfer (MMLCT) complexes. Photoexcitation activates the formation of a Pt-Pt bond, launching a stretching vibrational wavepacket. The molecular-structure-dependent decoherence and recoherence dynamics of this wavepacket resolve the spin-vibronic mechanism. We find that vectorial motion along the Pt-Pt stretching coordinates tunes the singlet and intermediate-state energy gap irreversibly towards the conical intersection and subsequently drives formation of the lowest stable triplet state in a ratcheting fashion. This work demonstrates the viability of using vibronic coherences as probes6-9 to clarify the interplay among spin, electronic and nuclear dynamics in spin-conversion processes, and this could inspire new modular designs to tailor the properties of excited states.

Revealing Excited-State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time.

Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited-state trajectories of a diplatinum complex featuring photo-activated metal-metal σ-bond formation and associated Pt-Pt stretching motions were detected in real time using femtosecond wide-angle X-ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt-Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited-state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non-equilibrium processes along excited-state trajectories involving multiple excited-state PESs.

Excited state processes of dinuclear Pt(II) complexes bridged by 8-hydroxyquinoline.

Dinuclear d8 Pt(II) complexes, where two mononuclear square planar Pt(II) units are bridged in an "A-frame" geometry, possess photophysical properties characterised by either metal-to-ligand-(MLCT) or metal-metal-ligand-to-ligand charge transfer (MMLCT) transitions determined by the distance between the two Pt(II) centres. When using 8-hydroxyquinoline (8HQH) as the bridging ligand to construct novel dinuclear complexes with general formula [C^NPt(µ-8HQ)]2, where C^N is either 2-phenylpyridine (1) or 7,8-benzoquinoline (2), triplet ligand-centered (3LC) photophysics results echoing that in a mononuclear model chromophore, [Pt(8HQ)2] (3). The lengthened Pt-Pt distances of 3.255 Å (1) and 3.243 Å (2) results in a lowest energy absorption centred around 480 nm assigned as having mixed LC/MLCT character by TD-DFT, mirroring the visible absorption spectrum of 3. Additionally, 1 and 2 exhibit 3LC photoluminescence with limited quantum yields (0.008) from broad transitions centred near 680 nm. Photoexcitation of 1-3 leads to an initially prepared excited state that relaxes within 15 ps to a 3LC excited state centred on the 8HQ bridge, which then persists for several microseconds. All the experimental results correspond well with DFT electronic structure calculations.

AlphaFlow: autonomous discovery and optimization of multi-step chemistry using a self-driven fluidic lab guided by reinforcement learning.

Closed-loop, autonomous experimentation enables accelerated and material-efficient exploration of large reaction spaces without the need for user intervention. However, autonomous exploration of advanced materials with complex, multi-step processes and data sparse environments remains a challenge. In this work, we present AlphaFlow, a self-driven fluidic lab capable of autonomous discovery of complex multi-step chemistries. AlphaFlow uses reinforcement learning integrated with a modular microdroplet reactor capable of performing reaction steps with variable sequence, phase separation, washing, and continuous in-situ spectral monitoring. To demonstrate the power of reinforcement learning toward high dimensionality multi-step chemistries, we use AlphaFlow to discover and optimize synthetic routes for shell-growth of core-shell semiconductor nanoparticles, inspired by colloidal atomic layer deposition (cALD). Without prior knowledge of conventional cALD parameters, AlphaFlow successfully identified and optimized a novel multi-step reaction route, with up to 40 parameters, that outperformed conventional sequences. Through this work, we demonstrate the capabilities of closed-loop, reinforcement learning-guided systems in exploring and solving challenges in multi-step nanoparticle syntheses, while relying solely on in-house generated data from a miniaturized microfluidic platform. Further application of AlphaFlow in multi-step chemistries beyond cALD can lead to accelerated fundamental knowledge generation as well as synthetic route discoveries and optimization.

Employing Long-Range Inductive Effects to Modulate Metal-to-Ligand Charge Transfer Photoluminescence in Homoleptic Cu(I) Complexes.

Four Cu(I) bis(phenanthroline) photosensitizers formulated from a new ligand structural motif (Cu1-Cu4) coded according to their 2,9-substituents were synthesized, structurally characterized, and fully evaluated using steady-state and time-resolved absorption and photoluminescence (PL) measurements as well as electrochemistry. The 2,9-disubstituted-3,4,7,8-tetramethyl-1,10-phenanthroline ligands feature the following six-membered ring systems prepared through photochemical synthesis: 4,4-dimethylcyclohexyl (1), tetrahydro-2H-pyran-4-yl (2), tetrahydro-2H-thiopyran-4-yl (3), and 4,4-difluorocyclohexyl (4). Universally, these Cu(I) metal-to-ligand charge transfer (MLCT) chromophores display excited-state lifetimes on the microsecond time scale at room temperature, including the three longest-lived homoleptic cuprous phenanthroline excited states measured to date in de-aerated CH2Cl2, τ = 2.5-4.3 µs. This series of molecules also feature high PL quantum efficiencies (ΦPL = 5.3-12% in CH2Cl2). Temperature-dependent PL lifetime experiments confirmed that all these molecules exhibit reverse intersystem crossing and display thermally activated delayed PL from a 1MLCT excited state lying slightly above the 3MLCT state, 1050-1490 cm-1. Ultrafast and conventional transient absorption measurements confirmed that the PL originates from the MLCT excited state, which remains sterically arrested, preventing an excessive flattening distortion even when dissolved in Lewis basic CH3CN. Combined PL and electrochemical data provided evidence that Cu1-Cu4 are highly potent photoreductants (Eox* = -1.73 to -1.62 V vs Fc+/0 in CH3CN), whose potentials are altered solely based on which heteroatoms or substituents are resident on the 2,9-appended ring derivatives. It is proposed that long-range electronic inductive effects are responsible for the systematic modulation observed in the PL spectra, excited-state lifetimes, and the ground state absorption spectra and redox potentials. Cu1-Cu4 quantitatively follow the energy gap law, correlating well with structurally related cuprous phenanthrolines and are also shown to triplet photosensitize the excited states of 9,10-diphenylanthracene with bimolecular rate constants ranging from 1.61 to 2.82 × 108 M-1 s-1. The ability to tailor both photophysical and electrochemical properties using long-range inductive effects imposed by the 2,9-ring platforms advocates new directions for future MLCT chromophore discovery.

Surface Immobilization of a Re(I) Tricarbonyl Phenanthroline Complex to Si(111) through Sonochemical Hydrosilylation.

A sonochemical-based hydrosilylation method was employed to covalently attach a rhenium tricarbonyl phenanthroline complex to silicon(111). fac-Re(5-(p-Styrene)-phen)(CO)3Cl (5-(p-styrene)-phen = 5-(4-vinylphenyl)-1,10-phenanthroline) was reacted with hydrogen-terminated silicon(111) in an ultrasonic bath to generate a hybrid photoelectrode. Subsequent reaction with 1-hexene enabled functionalization of remaining atop Si sites. Attenuated total reflectance-Fourier transform infrared spectroscopy confirms attachment of the organometallic complex to silicon without degradation of the organometallic core, supporting hydrosilylation as a strategy for installing coordination complexes that retain their molecular integrity. Detection of Re(I) and nitrogen by X-ray photoelectron spectroscopy (XPS) further support immobilization of fac-Re(5-(p-styrene)-phen)(CO)3Cl. Cyclic voltammetry and electrochemical impedance spectroscopy under white light illumination indicate that fac-Re(5-(p-styrene)-phen)(CO)3Cl undergoes two electron reductions. Mott-Schottky analysis indicates that the flat band potential is 239 mV more positive for p-Si(111) co-functionalized with both fac-Re(5-(p-styrene)-phen)(CO)3Cl and 1-hexene than when functionalized with 1-hexene alone. XPS, ultraviolet photoelectron spectroscopy, and Mott-Schottky analysis show that functionalization with fac-Re(5-(p-styrene)-phen)(CO)3Cl and 1-hexene introduces a negative interfacial dipole, facilitating reductive photoelectrochemistry.

Triplet Photosensitized para-Hydrogen Induced Polarization.

Despite its enormous utility in structural characterization, nuclear magnetic resonance (NMR) spectroscopy is inherently limited by low spin polarization. One method to address the low polarization is para-hydrogen (p-H2) induced polarization (PHIP) which uses the singlet spin isomer of H2 to generate disparate nuclear spin populations to amplify the associated NMR signals. PHIP often relies on thermal catalysis or, more infrequently, UV-activated catalytic hydrogenation. Light-activated hydrogenation enables direct and timed control over the hyperpolarization of target substrates, critical for identifying short-lived intermediates. Here, we use an established Ir(III) triplet photosensitizer (PS) to visible light sensitize the triplet ligand-field states in the d6-transition metal dihydride Ru(CO)(PPh3)3(H)2 (1). Excitation inside a 9.4 T NMR spectrometer with the PS and a 420 nm blue LED, under 3 atm of p-H2, successfully photosensitized hyperpolarization in 1 and in a range of unsaturated substrates at and below room temperature, up to 1630-fold. In otherwise identical experimental conditions without light activation, no polarization was realized in 1 or the substrates evaluated. We believe triplet-sensitized PHIP (Trip-PHIP) represents a facile experimental means for probing triplet sensitized light activation in transition metal catalysts possessing low-lying triplet ligand-field states, providing mechanistic insight of potentially tremendous value in chemical catalysis.

Real-Time and In Situ Viscosity Monitoring in Industrial Adhesives Using Luminescent Cu(I) Phenanthroline Molecular Sensors.

Monitoring the viscosity of polymers in real-time remains a challenge, especially in confined environments where traditional rheological measurements are hard to apply. In this study, we have utilized the luminescent complex [Cu(diptmp)2]+ (diptmp = 2,9-diisopropyl-3,4,7,8-tetramethyl-1,10-phenanthroline) as an optical probe for real-time sensing of viscosity in various adhesives during the curing process (viscosity increases). The emission lifetime of the triplet metal-to-ligand charge transfer (3MLCT) state of [Cu(diptmp)2]+ in epoxy adhesive increased exponentially during curing, similar to viscosity values obtained from oscillatory rheology. The longer lifetime in higher viscosity materials was attributed to changes in the excited-state deactivation processes from a known Jahn-Teller distortion in the Cu(I) geometry from tetrahedral in the ground state to square planar in the excited state. The real-time viscosity was also monitored reversibly by emission lifetime during polymer swelling (viscosity and lifetime decrease) and unswelling (viscosity and lifetime increase). Monitoring emission lifetime, unlike measuring the excited-state lifetime via transient absorption measurements in our previous study, allowed us to measure viscosity in opaque samples which scatter light. The optical probe [Cu(diptmp)2]+ in Gorilla Glue adhesive showed a clear correlation of the emission intensity or lifetime to viscosity during the curing process. We have also compared these lifetime changes using [Ru(bpy)3]2+ (bpy = bipyridine) as a control. [Cu(diptmp)2]+ showed not only a higher emission lifetime but also more ubiquity as a real-time viscosity sensor.

Ultrafast branching in intersystem crossing dynamics revealed by coherent vibrational wavepacket motions in a bimetallic Pt(II) complex.

Ultrafast excited state processes of transition metal complexes (TMCs) are governed by complicated interplays between electronic and nuclear dynamics, which demand a detailed understanding to achieve optimal functionalities of photoactive TMC-based materials for many applications. In this work, we investigated a cyclometalated platinum(II) dimer known to undergo a Pt-Pt bond contraction in the metal-metal-to-ligand-charge-transfer (MMLCT) excited state using femtosecond broadband transient absorption (fs-BBTA) spectroscopy in combination with geometry optimization and normal mode calculations. Using a sub-20 fs pump and broadband probe pulses in fs-BBTA spectroscopy, we were able to correlate the coherent vibrational wavepacket (CVWP) evolution with the stimulated emission (SE) dynamics of the 1MMLCT state. The results demonstrated that the 145 cm-1 CVWP motions with the damping times of ∼0.9 ps and ∼2 ps originate from coherent Pt-Pt stretching vibrations in the singlet and triplet MMLCT states, respectively. On the basis of excited state potential energy surface calculations in our previous work, we rationalized that the CVWP transfer from the Franck-Condon (FC) state to the 3MMLCT state was mediated by a triplet ligand-centered (3LC) intermediate state through two step intersystem crossing (ISC) on a time scale shorter than a period of the Pt-Pt stretching wavepacket motions. Moreover, it was found that the CVWP motion had 110 cm-1 frequency decays with the damping time of ∼0.2 ps, matching the time constant of 0.253 ps, corresponding to a redshift in the SE feature at early times. This observation indicates that the Pt-Pt bond contraction changes the stretching frequency from 110 to 145 cm-1 and stabilizes the 1MMLCT state relative to the 3LC state with a ∼0.2 ps time scale. Thus, the ultrafast ISC from the 1MMLCT to the 3LC states occurs before the Pt-Pt bond shortening. The findings herein provide insight into understanding the impact of Pt-Pt bond contraction on the ultrafast branching of the 1MMLCT population into the direct (1MMLCT → 3MMLCT) and indirect ISC pathways (1MMLCT → 3LC → 3MMLCT) in the Pt(II) dimer. These results revealed intricate excited state electronic and nuclear motions that could steer the reaction pathways with a level of detail that has not been achieved before.

Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence.

Photoluminescent molecules exploiting the sizable spin-orbit coupling constants of main group metals and metalloids to access long-lived triplet excited states are relatively rare compared to phosphorescent transition metal complexes. Here we report the synthesis of three air- and moisture-stable group 14 compounds E(MePDPPh)2, where E = Si, Ge, or Sn and [MePDPPh]2- is the doubly deprotonated form of 2,6-bis(5-methyl-3-phenyl-1H-pyrrol-2-yl)pyridine. In solution, all three molecules exhibit exceptionally long-lived triplet excited states with lifetimes in the millisecond range and show highly efficient photoluminescence (Φ ≤ 0.49) due to competing prompt fluorescence and thermally activated delayed fluorescence at and around room temperature. Temperature-dependent steady-state emission spectra and photoluminescent lifetime measurements provided conclusive evidence for the two distinct emission pathways. Picosecond transient absorption spectroscopy allowed further analysis of the intersystem crossing (ISC) between singlet and triplet manifolds (τISC = 0.25-3.1 ns) and confirmed the expected trend of increased ISC rates for the heavier elements in otherwise isostructural compounds.

A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids.

Aryl halides are a fundamental motif in synthetic chemistry, playing a critical role in metal-mediated cross-coupling reactions and serving as important scaffolds in drug discovery. Although thermal decarboxylative functionalization of aryl carboxylic acids has been extensively explored, the scope of existing halodecarboxylation methods remains limited, and there currently exists no unified strategy that provides access to any type of aryl halide from an aryl carboxylic acid precursor. Herein, we report a general catalytic method for direct decarboxylative halogenation of (hetero)aryl carboxylic acids via ligand-to-metal charge transfer. This strategy accommodates an exceptionally broad scope of substrates. We leverage an aryl radical intermediate toward divergent functionalization pathways: (1) atom transfer to access bromo- or iodo(hetero)arenes or (2) radical capture by copper and subsequent reductive elimination to generate chloro- or fluoro(hetero)arenes. The proposed ligand-to-metal charge transfer mechanism is supported through an array of spectroscopic studies.

Thermally Activated Bright-State Delayed Blue Photoluminescence from InP Quantum Dots.

Thermally activated delayed photoluminescence (TADPL) generated from organic chromophore-functionalized quantum dots (QDs) is potentially beneficial for persistent light generation, QD-based PL sensors, and photochemical synthesis. While previous research demonstrated that naphthoic acid-functionalized InP QDs can be employed as low-toxicity, blue-emissive TADPL materials, the electron trap states inherent in these nanocrystals inhibited the observation of TADPL emerging from the higher-lying bright states. Here, we address this challenge by employing the heterocyclic aromatic compound 8-quinolinecarboxylic acid (QCA), whose triplet energy is strategically positioned to bypass the electron trap states in InP QDs. Transient absorption and photoluminescence spectroscopies revealed the generation of bright-state TADPL from QCA-functionalized InP QDs resulting from a nearly quantitative Dexter-like triplet-triplet energy transfer (TTET) from photoexcited InP QDs to surface-anchored QCA chromophores followed by reverse TTET from these bound molecules to the InP QDs. This modification resulted in a 119-fold increase in the average PL intensity decay time with respect to the as-synthesized InP QDs.

Copper(II)-photocatalyzed decarboxylative oxygenation of carboxylic acids.

Showcasing the concept of light-induced homolysis for the generation of radicals, the CuII-photocatalyzed decarboxylative oxygenation of carboxylic acids with molecular oxygen as the terminal oxidant is described. Two CuII-carboxylate complexes with different coordination geometries were synthesized and characterized by X-ray analysis, correlating their structure with their ability to initiate light-induced decarboxylations.

Engineering Long-Lived Blue Photoluminescence from InP Quantum Dots Using Isomers of Naphthoic Acid.

Leveraging triplet excitons in semiconductor quantum dots (QDs) in concert with surface-anchored molecules to produce long-lifetime thermally activated delayed photoluminescence (TADPL) continues to emerge as a promising technology in diverse areas including photochemical catalysis and light generation. All QDs presently used to generate TADPL in QD/molecule constructs contain toxic metals including Cd(II) and Pb(II), ultimately limiting potential real-world applications. Here, we report newly conceived blue-emitting TADPL-producing nanomaterials featuring InP QDs interfaced with 1- and 2-naphthoic acid (1-NA and 2-NA) ligands. These constitutional isomers feature similar triplet energies but disparate triplet lifetimes, translating into InP-based TADPL processes displaying two distinct average lifetime ranges upon cooling from 293 to 193 K. The time constants fall between 4.4 and 59.2 µs in the 2-NA-decorated InP QDs while further expanding between 84.2 and 733.2 µs in the corresponding 1-NA-ligated InP materials, representing a 167-fold time window. The resulting long-lived excited states enabled facile bimolecular triplet sensitization of 1O2 phosphorescence in the near-IR and promoted sensitized triplet-triplet annihilation photochemistry in 2,5-diphenyloxazole. We speculate that the discovery of new nanomaterials exhibiting TADPL lies on the horizon as myriad QDs can be readily derivatized using isomers of numerous classes of surface-anchoring chromophores yielding precisely regulated photophysical properties.

Metal-Metal-to-Ligand Charge Transfer in Pt(II) Dimers Bridged by Pyridyl and Quinoline Thiols.

The investigation of two distinct species of square planar dinuclear Pt(II) dimers based on anti-[Pt(C∧N)(µ-N∧S)]2, where C∧N is either 2-phenylpyridine (ppy) or benzo(h)quinoline (bzq) and N∧S is pyridine-2-thiol (pyt), 6-methylpyridine-2-thiol (Mpyt), or 2-quinolinethiol (2QT), is presented. Each molecule was thoroughly characterized with electronic structure calculations, static UV-vis and photoluminescence (PL) spectroscopy, and cyclic voltammetry, along with transient absorbance and time-gated PL experiments. These visible absorbing chromophores feature metal-metal-to-ligand charge-transfer (MMLCT) excited states that originate from intramolecular d8-d8 metal-metal σ-interactions and are manifested in the ground- and excited-state properties of these molecules. All five molecules reported (anti-[Pt(ppy)(µ-Mpyt)]2 could not be isolated), three of which are newly conceived here, possess electronic absorptions past 500 nm and high quantum yield PL emission with spectra extending into the far red (λem > 700 nm), originating from the charge-transfer state in each instance. Each chromophore displays excited-state decay kinetics adequately modeled by single exponentials as recorded using dynamic absorption and PL experiments; each technique yields similar decay kinetics. The combined data illustrate that pyridyl and quinoline-thiolates in conjunction with select cyclometalates represent classes of MMLCT chromophores that exhibit excited-state properties suitable for promoting light-energized chemical reactions and provide a molecular platform suitable for evaluating coherence phenomena in transient metal-metal bond-forming photochemistry.

Photochemical H2 Evolution from Bis(diphosphine)nickel Hydrides Enables Low-Overpotential Electrocatalysis.

Molecules capable of both harvesting light and forming new chemical bonds hold promise for applications in the generation of solar fuels, but such first-row transition metal photoelectrocatalysts are lacking. Here we report nickel photoelectrocatalysts for H2 evolution, leveraging visible-light-driven photochemical H2 evolution from bis(diphosphine)nickel hydride complexes. A suite of experimental and theoretical analyses, including time-resolved spectroscopy and continuous irradiation quantum yield measurements, led to a proposed mechanism of H2 evolution involving a short-lived singlet excited state that undergoes homolysis of the Ni-H bond. Thermodynamic analyses provide a basis for understanding and predicting the observed photoelectrocatalytic H2 evolution by a 3d transition metal based catalyst. Of particular note is the dramatic change in the electrochemical overpotential: in the dark, the nickel complexes require strong acids and therefore high overpotentials for electrocatalysis; but under illumination, the use of weaker acids at the same applied potential results in a more than 500 mV improvement in electrochemical overpotential. New insight into first-row transition metal hydride photochemistry thus enables photoelectrocatalytic H2 evolution without electrochemical overpotential (at the thermodynamic potential or 0 mV overpotential). This catalyst system does not require sacrificial chemical reductants or light-harvesting semiconductor materials and produces H2 at rates similar to molecular catalysts attached to silicon.