James E. Yarnell

Two novel dinuclear Pt(ii) complexes featuring 8-hydroxyquinoline bridges were synthesized and found to have photophysical properties dominated by ligand-centered transitions mirroring that of a mononuclear model system, [Pt(8HQ)₂].

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 (λ_em > 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.

Modulating electronic and geometric structure of perinone chromophores is easily achieved via systematic alteration of aromatic diamine and anhydride building blocks, eliciting deterministic photoredox and excited state dynamical properties.

The steady-state and ultrafast to supra-nanosecond excited state dynamics of fac-[Re(NBI-phen)(CO)₃(L)](PF₆) (NBI-phen = 16H-benzo[4′,5′]isoquinolino[2′,1′:1,2]imidazo[4,5-f][1,10]phenanthrolin-16-one) as well as their respective models of the general molecular formula [Re(phen)(CO)₃(L)](PF₆) (L = PPh₃ and CH₃CN) has been investigated using transient absorption and time-gated photoluminescence spectroscopy. The NBI-phen containing molecules exhibited enhanced visible light absorption with respect to their models and a rapid formation (<6 ns) of the triplet ligand-centred (LC) excited state of the organic ligand, NBI-phen. These triplet states exhibit an extended excited state lifetime that enable the energized molecules to readily engage in triplet–triplet annihilation photochemistry.

The manipulation of the triplet excited state manifold leads to large differences in the photophysical properties within a given class of metal–organic chromophores. By the appropriate choice of ancillary ligand, large changes can be made both to the order and nature of the lowest excited states and therefore to the resulting photophysical properties. Herein, a series of four bis-2-phenylpyridine (ppy) cyclometalated Ir(III) compounds bearing two arylisocyanide ligands were synthesized and photophysically characterized to understand the effects of using ancillary ligands featuring systematic changes in π-conjugation. By varying the arylisocyanide ligands, the photoluminescence quantum yield ranged from 5% to 49% and the excited state lifetime ranged between 24 μs and 2 ms. These variations in photophysical response are consistent with lowering the triplet ligand-centered (³LC) state of the arylisocyanide ligand as the π system was extended, confirmed by 77 K photoluminescence emission spectra and ultrafast transient absorption experiments. The latter analysis gleaned detailed insight into the importance of the interplay of the ³LC state of the phenylpyridine and arylisocyanide ligands in these polychromophic Ir(III) molecules.

Metal-free chromophores that efficiently generate triplet excited states represent promising alternatives with respect to transition metal-containing photosensitizers, such as those featuring metal-to-ligand charge transfer excited states. However, such molecular constructs have remained underexplored due to the unclear relationship(s) between molecular structure and efficient/rapid intersystem crossing. In this regard, we present a series of three thionated perinone chromophores serving as a newly conceived class of heavy metal-free triplet photosensitizers. We demonstrate that thionation of the lone C═O substituent in each highly fluorescent perinone imparts red-shifted absorbance bands that maintain intense extinction coefficients across the visible spectrum, as well as unusually efficient triplet excited state formation as inferred from the measured singlet O₂ quantum yields at 1270 nm (Φ_Δ = 0.78–1.0). Electronic structure calculations revealed the emergence of a low energy S₁ (n → π*) excited state in the proximity of a slightly higher energy S₂ (π → π*) excited state. The distinct character in each of the two lowest-lying singlet state manifolds resulted in the energetic inversion of the corresponding triplet excited states due to differences in electron exchange interactions. Rapid S₁ → T₁ intersystem crossing was thereby facilitated in this manner through spin–orbit coupling as predicted by the El Sayed rules. The lifetimes of the resultant triplet excited states persisted into the microsecond time regime, as measured by transient absorbance spectroscopy, enabling effective bimolecular triplet sensitization of some common polycyclic aromatic hydrocarbons. The synthetically facile interchange of a single O atom to an S atom in the investigated perinones resulted in marked changes to their photophysical properties, namely, conversion of dominant singlet state fluorescence in the former to long-lived triplet excited states in the latter. The combined results suggest a general strategy for accessing long-lived triplet excited states in organic chromophores featuring a lone C═O moiety residing within its structure, valuable for the design of metal-free triplet photosensitizers.

We present the synthesis, structural characterization, electronic structure calculations, and ultrafast and supra-nanosecond photophysical properties of a series of five Re(I) bichromophores exhibiting metal to ligand charge transfer (MLCT) excited states based on the general formula fac-[Re(N^∧N)(CO)₃(PNI-py)]PF_6, where PNI-py is 4-piperidinyl-1,8-naphthalimidepyridine and N^∧N is a diimine ligand (Re1–5), along with their corresponding model chromophores where 4-ethylpyridine was substituted for PNI-py (Mod1–5). The diimine ligands used include 1,10-phenanthroline (phen, 1), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bcp, 2), 4,4′-di-tert-butyl-2,2′-bipyridine (dtbb, 3), 4,4′-diethyl ester-2,2′-bipyridine (deeb, 4), and 2,2′-biquinoline (biq, 5). In these metal–organic bichromophores, structural modification of the diimine ligand resulted in substantial changes to the observed energy transfer efficiencies between the two chromophores as a result of the variation in ³MLCT excited-state energies. The photophysical properties and energetic pathways of the model chromophores were investigated in parallel to accurately track the changes that arose from introduction of the organic chromophore pendant on the ancillary ligand. All relevant photophysical and energy transfer processes were probed and characterized using time-resolved photoluminescence spectroscopy, ultrafast and nanosecond transient absorption spectroscopy, and time-dependent density functional theory calculations. Of the five bichromophores in this study, four (Re1–4) exhibited a thermal equilibrium between the ³PNI-py and the ³MLCT excited state, drastically extending the lifetimes of the parent model chromophores.

We present the synthesis, structural characterization, electronic structure calculations, and the ultrafast and supra-nanosecond photophysical properties of a series of five bichromophores of the general structural formula [Re(5-R-phen)(CO)₃(dmap)](PF₆), where R is a naphthalimide (NI), phen = 1,10-phenanthroline, and dmap is 4-dimethylaminopyridine. The NI chromophores were systematically modified at their 4-positions with -H (NI), -Br (BrNI), phenoxy (PONI), thiobenzene (PSNI), and piperidine (PNI), rendering a series of metal–organic bichromophores (Re1–Re5, respectively) featuring variability in the singlet and triplet energies in the pendant NI subunit. Five closely related organic chromophores as well as [Re(phen)(CO)₃(dmap)](PF₆) (Re6) were investigated in parallel to appropriately model the photophysical properties exhibited in the bichromophores. The excited state processes of all molecules in this study were elucidated using a combination of transient absorption spectroscopy and time-resolved photoluminescence (PL) spectroscopy, revealing the kinetics of the energy transfer processes occurring between the appended chromophores. The spectroscopic analysis was further supported by electronic structure calculations which identified the origin of many of the experimentally observed electronic transitions.

We present a series of four transition-metal complexes based on the rhenium(I) tricarbonyl 1,10-phenanthroline (phen) template, with a lone ancillary arylisocyanide (CNAr) ligand to yield metal–organic chromophores of the generic molecular formula [Re(phen)(CO)₃(CNAr)]⁺ [CNAr = 2,6-diisopropylphenyl isocyanide (1), 4-phenyl-2,6-diisopropylphenyl isocyanide (2), 4-phenylethynyl-2,6-diisopropylphenyl isocyanide (3), and 4-biphenyl-2,6-diisopropylphenyl isocyanide (4)]. This particular series features varied degrees of π-conjugation length in the CNAr moiety, resulting in significant modulation in the resultant photophysical properties. All molecules possess long-lived [8–700 μs at room temperature (RT)], strongly blue-green photoluminescent and highly energetic excited states (λ_max,em = 500–518 nm; Φ = 14–64%). Each of these chromophores has been photophysically investigated using static and dynamic spectroscopic techniques, the latter probed from ultrafast to supra-nanosecond time scales using transient absorption and photoluminescence (PL). Time-resolved PL intensity decays recorded as a function of the temperature were consistent with the presence of at least two emissive states lying closely spaced in energy with a third nonemissive state lying much higher in energy and likely ligand-field in character. The combined experimental evidence, along with the aid of electronic structure calculations (density functional theory and time-dependent density functional theory performed at the M06/Def2-SVP/SDD level), illustrates that the CNAr ligand is actively engaged in manipulating the excited-state decay in three of these molecules (2–4), wherein the triplet metal-to-ligand charge-transfer (³MLCT) state along with two distinct triplet ligand-centered (³LC) excited-state configurations (phen and CNAr) conspire to produce the resultant photophysical properties. Because the π conjugation within the CNAr ligand was extended, an interesting shift in the dominant photophysical processes was observed. When the CNAr conjugation length is short, as in 1, the phenanthroline ³LC state dominates, resulting in a configurationally mixed triplet excited state of both LC and MLCT character. With more extended π conjugation in the CNAr subunit (2–4), the initially generated ³LC(phen)/³MLCT excited state ultimately migrates to the CNAr ³LC state on the order of tens of picoseconds. Molecules 3 and 4 in this series also feature unique examples of inorganic excimer formation, as evidenced by dynamic self-quenching in the corresponding PL intensity decays accompanied by the observation of a short-lived low-energy emission feature.