Triplet excitons are pervasive in both organic and inorganic semiconductors but generally remain confined to the material in which they originate. We demonstrated by transient absorption spectroscopy that cadmium selenide semiconductor nanoparticles, selectively excited by green light, engage in interfacial Dexter-like triplet-triplet energy transfer with surface-anchored polyaromatic carboxylic acid acceptors, extending the excited-state lifetime by six orders of magnitude. Net triplet energy transfer also occurs from surface acceptors to freely diffusing molecular solutes, further extending the lifetime while sensitizing singlet oxygen in an aerated solution. The successful translation of triplet excitons from semiconductor nanoparticles to the bulk solution implies that such materials are generally effective surrogates for molecular triplets. The nanoparticles could thereby potentially sensitize a range of chemical transformations that are relevant for fields as diverse as optoelectronics, solar energy conversion, and photobiology.

Synthetic organic chemistry has seen major advances due to the merger of nickel and photoredox catalysis. A growing number of Ni-photoredox reactions are proposed to involve generation of excited nickel species, sometimes even in the absence of a photoredox catalyst. To gain insights about these excited states, two of our groups previously studied the photophysics of Ni­( t‑Bubpy)­(o-Tol)­Cl, which is representative of proposed intermediates in many Ni-photoredox reactions. This complex was found to have a long-lived excited state (τ = 4 ns), which was computationally assigned as a metal-to-ligand charge transfer (MLCT) state with an energy of 1.6 eV (38 kcal/mol). This work evaluates the computational assignment experimentally using a series of related complexes. Ultrafast UV–Vis and mid-IR transient absorption data suggest that a MLCT state is generated initially upon excitation but decays to a long-lived state that is 3d-d rather than 3MLCT in character. Dynamic cis,trans-isomerization of the square planar complexes was observed in the dark using 1H NMR techniques, supporting that this 3d-d state is tetrahedral and accessible at ambient temperature. Through a combination of transient absorption and NMR studies, the 3d-d state was determined to lie ∼0.5 eV (12 kcal/mol) above the ground state. Because the 3d-d state features a weak Ni–aryl bond, the excited Ni­(II) complexes can undergo Ni homolysis to generate aryl radicals and Ni­(I), both of which are supported experimentally. Thus, photoinduced Ni–aryl homolysis offers a novel mechanism of initiating catalysis by Ni­(I).

Subpicosecond through supra-nanosecond transient absorption dynamics of the homoleptic Cu(I) metal-to-ligand charge transfer (MLCT) photosensitizers including the benchmark [Cu(dmp)2](+) (dmp =2,9-dimethyl-1,10-phenanthroline) chromophore, as well as [Cu(dsbp)2](+) (dsbp =2,9-di(sec-butyl)-1,10-phenanthroline and [Cu(dsbtmp)2](+) (dsbtmp =2,9-di(sec-butyl)-3,4,7,8-tetramethyl-1,10-phenanthroline) were investigated in dichloromethane and tetrahydrofuran solutions. Visible and near-IR spectroelectrochemical measurements of the singly reduced [Cu(dsbp)2](+) and [Cu(dsbtmp)2](+) species were determined in tetrahydrofuran, allowing for the identification of redox-specific phenanthroline-based radical anion spectroscopic signatures prevalent in the respective transient absorption experiments. This study utilized four different excitation wavelengths (418, 470, 500, and 530 nm) to elucidate dynamics on ultrafast times scales spanning probe wavelengths ranging from the UV to the near-IR (350 to 1450 nm). With the current time resolution of ∼150 fs, initial excited state decay in all three compounds was found to be independent of excitation wavelength. Not surprisingly, there was little to no observed influence of solvent in the initial stages of excited state decay in any of these molecules including [Cu(dmp)2](+), consistent with results from previous investigators. The combined experimental data revealed two ranges of time constants observed on short time scales in all three MLCT chromophores and both components lengthen as a function of structure in the following manner: [Cu(dsbtmp)2](+) < [Cu(dsbp)2](+) < [Cu(dmp)2](+). The molecule with the most inhibited potential for distortion, [Cu(dsbtmp)2](+), possessed the fastest ultrafast dynamics as well as the longest excited state lifetimes in both solvents. These results are consistent with a small degree of excited state distortion, rapid intersystem crossing, and weak vibronic coupling to the ground state. The concomitant systematic variation in both initial time constants, assigned to pseudo-Jahn-Teller distortion and intersystem crossing, suggest that both processes are intimately coupled in all molecules in the series. The variability in these time scales illustrate that strongly impeded structural distortion in Cu(I) MLCT excited state enables more rapid surface crossings in the initial deactivation dynamics.

The generation and transfer of triplet excitons across the molecular-semiconductor interface represents an important technological breakthrough featuring numerous fundamental scientific questions. This contribution demonstrates curious delayed formation of TIPS-pentacene molecular triplet excitons bound on the surface of PbS nanocrystals mediated through the initial production of a proposed charge transfer intermediate following selective excitation of the PbS quantum dots. Ultrafast UV-vis and near-IR transient absorption spectroscopy was used to track the dynamics of the initial PbS exciton quenching as well as time scale of the formation of molecular triplet excited states that persisted for 10 μs on the PbS surface, enabling subsequent energy and electron transfer reactivity. These results provide the pivotal proof-of-concept that PbS nanocrystals absorbing near-IR radiation can ultimately generate molecular triplets on their surfaces through processes distinct from direct Dexter triplet energy transfer. More broadly, this work establishes that small metal chalcogenide semiconductor nanocrystals interfaced with molecular chromophores exhibit behavior reminiscent of supramolecular chemical systems, a potentially impactful concept for nanoscience.

In the interest of expanding the inventory of available long lifetime, photochemically robust, and strongly reducing Cu(I) MLCT sensitizers, we present detailed structural, photophysical, and electrochemical characterization of [Cu(dipp)], dipp = 2,9-diisopropyl-1,10-phenanthroline, and its sterically encumbered tetramethyl analogue [Cu(diptmp)], diptmp = 2,9-diisopropyl-3,4,7,8-tetramethyl-1,10-phenanthroline. The achiral isopropyl substituents enable similar steric bulk effects to the previously investigated sec-butyl substituents while eliminating the complex NMR structural analyses associated with the presence of two chiral centers in the latter. The photophysical properties of [Cu(diptmp)] are impressive, possessing a 2.3 μs lifetime in deaerated CHCl and a photoluminescence quantum yield of 4.7%, which were slightly attenuated in coordinating tetrahydrofuran (THF) solutions. Nanosecond transient absorption spectroscopy results matched the transient photoluminescence kinetics enabling complete characterization of MLCT excited-state decay in these molecules. The calculated excited-state potential for the Cu/Cu* couple (E = -1.74 V vs Fc) indicated that [Cu(diptmp)]* is a strong photoreductant potentially useful for myriad applications. Ultrafast transient absorption measurements performed in THF solutions are also reported, yielding the relative time scales for both the pseudo-Jahn-Teller distortion (0.4-0.8 ps in [Cu(dipp)] and 0.12-0.5 ps in [Cu(diptmp)]) and singlet-triplet intersystem crossing (6.4-10.1 ps for [Cu(dipp)] and 3.5-5.4 ps for [Cu(diptmp)]) within these molecules. The disparity in the time scales of pseudo-Jahn-Teller distortion and intersystem crossing between two complexes with different anticipated excited-state geometries suggests that strongly impeded structural distortion in the MLCT excited state (i.e., [Cu(diptmp)]) enables more rapid surface crossings in the initial deactivation dynamics.