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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 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 (

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(

The investigation of two distinct species of square planar dinuclear Pt(II) dimers based on

In this work, a series of nine Re(i) diimine dicarbonyl complexes of the general molecular formula cis-[Re(N^N)2(CO)2]+ (N^N are various 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) derivatives) were prepared and spectroscopically investigated to systematically evaluate the photophysical consequences of various substituents resident on the diimine ligands. These panchromatic absorbing chromophores were structurally characterized, evaluated for their electrochemical and spectroelectrochemical properties, and investigated using static and dynamic electronic absorption, photoluminescence (PL), and infrared spectroscopy from ultrafast to supra-nanosecond time scales. The ultrafast time-resolved infrared (TRIR) analysis was further supported by electronic structure calculations which characterized the changes within the two C[triple bond, length as m-dash]O vibrational modes upon formation of the metal-to-ligand charge transfer (MLCT) excited state. The MLCT excited state decay of this series of dicarbonyl molecules appears completely consistent with energy-gap law behavior, where the nonradiative decay rate constants increase logarithmically with decreasing excited state - ground state energy separation, except in anticipated cases where the substituents were phenyl or tert-butyl.

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.

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)

A new long-lived, visible-light-absorbing homoleptic Cu(I) metal-to-ligand charge transfer (MLCT) photosensitizer, [Cu(dchtmp)2]PF6 (dchtmp = 2,9-dicyclohexyl-3,4,7,8-tetramethyl-1,10-phenanthroline), has been synthesized, structurally characterized, and evaluated in terms of its molecular photophysics, electrochemistry, and electronic structure. Static and time-resolved transient absorption (TA) and photoluminescence (PL) spectroscopy measured on the title compound in CH2Cl2 (τ = 2.6 μs, ΦPL = 5.5%), CH3CN (τ = 1.5 μs, ΦPL = 2.6%), and THF (τ = 2.0 μs, ΦPL = 3.7%) yielded impressive photophysical metrics even when dissolved in Lewis basic solvents. The combined static spectroscopic data along with ultrafast TA experiments revealed that the pseudo-Jahn-Teller distortion and intersystem crossing dynamics in the MLCT excited state displayed characteristics of being sterically arrested throughout its evolution. Electrochemical and static PL data illustrate that [Cu(dchtmp)2]PF6 is a potent photoreductant (-1.77 V vs Fc+/0 in CH3CN) equal to or greater than all previously investigated homoleptic Cu(I) diimine complexes. Although we successfully prepared the cyclopentyl analog dcptmp (2,9-dicyclopentyl-3,4,7,8-tetramethyl-1,10-phenanthroline) using the same C-C radical coupling photochemistry as dchtmp, the corresponding Cu(I) complex could not be isolated due to the steric hindrance presented at the metal center. Ultimately, the successful preparation of [Cu(dchtmp)2]+ represents a major step forward for the design and discovery of novel earth-abundant photosensitizers made possible through a newly conceived ligand synthetic strategy.

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)]PF6, 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.

A computationally inspired Cu(I) metal-to-ligand charge transfer (MLCT) chromophore, [Cu(sbmpep)2]+ (sbmpep = 2,9-di(sec-butyl)-3,8-dimethyl-4,7-di(phenylethynyl)-1,10-phenanthroline), was synthesized in seven total steps, prepared from either dichloro- or dibromophenanthroline precursors. Complete synthesis, structural characterization, and electrochemistry, in addition to static and dynamic photophysical properties of [Cu(sbmpep)2]+, are reported on all relevant time scales. UV–Vis absorption spectroscopy revealed significant increases in oscillator strength along with a concomitant bathochromic shift in the MLCT absorption bands with respect to structurally related model complexes (e = 16 500 M–1 cm–1 at 491 nm). Strong red photoluminescence (Φ = 2.7%, λmax = 687 nm) was observed from [Cu(sbmpep)2]+, which featured an average excited-state lifetime of 1.4 μs in deaerated dichloromethane. Cyclic and differential pulse voltammetry revealed ∼300 mV positive shifts in the measured one-electron reversible r...

The electronic structure and photophysical properties of two phosphorescent iridium(III) cyclometalated complexes is presented. The molecules were synthesized by cyclometalating the ligand 1,8-naphthalenebenzimidizole (NBI), to an iridium(III) metal center. Two NBI ligands were covalently attached along with a 1,10-phenanthroline (phen) ligand producing the [Ir(NBI)2(phen)](PF6) complex and three NBI ligands were used to prepare the corresponding tris-cyclometalate fac-Ir(NBI)3. The optical properties of these new Ir(III) molecules were investigated using density functional theory calculations, photoluminescence spectroscopy, and transient absorption spectroscopy. The molecules at the heart of this study were found to contain long-lived ligand-localized triplet excited states on the NBI species, featuring energies suitable for bimolecular photochemical reactions. Both iridium(III) chromophores possess excellent light absorptivity in the visible region of the spectrum with high photoluminescence quantum efficiencies approaching 30%.

When designing photoresponsive materials, the impact of a polymer host matrix on the photophysical and photochemical properties of chromophores can be dramatic and advantageous for correlating macromolecular properties. Some compounds possess changes in their photophysical response with variation in the surrounding media (e.g., crystalline glass vs solution). This study demonstrates how changes in the excited state dynamics of [Cu(dmp)2]+, where dmp = 2,9-dimethyl-1,10-phenanthroline, are used to quantitatively probe the viscosity of the surrounding polymer matrix. A correlation of both excited state lifetime and photoluminescence emission wavelength on viscosity was observed in different supramolecular materials containing [Cu(dmp)2]+. These effects were attributed to restricted photoinduced structural distortion of the Cu(I) complex as the polymer matrix hardened. This photoluminescence sensor features a greater dynamic range for viscosity sensing (6 orders of magnitude) and displayed larger changes in ...

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)2]+, dipp = 2,9-diisopropyl-1,10-phenanthroline, and its sterically encumbered tetramethyl analogue [Cu(diptmp)2]+, 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)2]+ are impressive, possessing a 2.3 μs lifetime in deaerated CH2Cl2 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 complet...

In the context of our work on main group-based anion sensors, we have synthesized the bromide salts of a series of tetraarylstibonium cations of general formula [ArSbPh3]+ with Ar = 9-phenanthryl ([1]+), 1-pyrenyl- ([2]+), and 3-perylenyl ([3]+). While [1]+ is not stable in water, we found that [2]+ and [3]+ can be used as sensors for the sub-ppm detection of fluoride anions in aqueous solutions consisting of 9/1 (v/v) H2O/DMSO (pH 4.8). Fluoride sensing, which rests on the formation of the fluorostiboranes 2–F and 3–F, is accompanied by a distinct turn-on fluorescence response. This response is especially marked upon conversion of [3]+ into 3–F, with a fluorescence intensity enhancement by ∼8 fold and a quantum yield of 59.2% for 3–F. The relevance of this study is established by demonstrating that [3]+ can be used as a selective fluoride sensor for bottle or tap water.

The electronic structure and photophysical properties of a luminescent IrIII bis-cyclometalated complex covalently attached to one 4-piperidinyl-1,8-naphthalimide (PNI) chromophore through a coordinated 1,10-phenanthroline, [Ir(ppy)2(phen-PNI)](PF6), is presented. This bichromophore represents a new class of visible light-harvesting IrIII complexes that exhibit markedly enhanced room-temperature excited-state lifetimes (τ = 8.8 ms) as a result of intervening ligand-centered triplet states present on the pendant naphthalimide chromophore. In this IrIII complex, the intense singlet fluorescence of the pendant PNI chromophore is nearly quantitatively quenched and was found to sensitize the IrIII metal/ligand-to-ligand charge-transfer (MLLCT) excited state. The excited state ultimately returns to the PNI chromophore as a long-lived excited triplet that disposes of its energy by equilibrating with the photoluminescent IrIII MLLCT excited state. Evidence of the excited-state equilibrium is provided through static and dynamic photoluminescence spectroscopy, transient absorption spectroscopy, and time-dependent density functional theory calculations.

The current investigation compares the photochemical upconversion sensitization properties of two long lifetime Cu(I) metal-to-ligand charge transfer (MLCT) chromophores to 3 distinct anthryl-based triplet acceptors. The sensitizers [Cu(dsbtmp)2](PF6) (1, dsbtmp = 2,9-di(sec-butyl)-3,4,7,8-tetramethyl-1,10-phenanthroline) and [Cu(dsbp)2](PF6) (2, dsbp = 2,9-di(sec-butyl-1,10-phenanthroline) were selectively excited in the presence of anthracene, 9,10-diphenylanthracene (DPA), and 9,10-dimethylanthracene (DMA) in degassed dichloromethane solutions. In all instances, triplet energy transfer was observed from selective excitation of the Cu(I) MLCT chromophore to each respective anthryl species. The bimolecular triplet-triplet energy transfer quenching rate constants were extracted from dynamic Stern-Volmer analyses in each case, yielding values below the diffusion limit in dichloromethane. However, the Stern-Volmer quenching constants (KSV's) were sizable enough (up to ∼2300 M(-1) with 1 as a sensitizer) to support efficient photochemical upconversion. As such, visible to near-UV photochemical upconversion was observed in every instance, along with the anticipated quadratic-to-linear incident light power dependence when pumping at 488 nm. The latter verified that it is indeed sensitized triplet-triplet annihilation responsible for the generation of the anthryl-based singlet fluorescence. Photochemical upconversion quantum efficiencies were evaluated using a relative actinometric method as both a function of incident light power density as well as anthryl acceptor/annihilator concentration. When 1 was used as the sensitizer, upconversion quantum yields as large as 9.2% and 17.8% were observed for DMA and DPA, respectively. Finally, the combination of 1 with DMA was shown to be quite robust, showing no obvious signs of decomposition during 12 h of continuous 488 nm photolysis.

Inorganic semiconductor quantum dot-molecular constructs represent an emerging class of materials functioning as triplet photosensitizers. Fundamental investigations into the exciton transfer/transduction processes at the interface of these hybrid materials have revealed parallels in the operable mechanisms to those established in purely molecular systems. The similarities in the governing energy migration mechanisms in these quantum-confined materials permit conventional photophysical strategies to be implemented in future research endeavors. This Viewpoint provides a perspective on this emerging field of inorganic quantum dots as photosensitizers, in particular the transfer of triplet excitons at the molecule-nanomaterial interface. The current state-of-the-art will be explored while highlighting areas of potential growth toward exploiting these materials in photofunctional solar energy conversion schemes.

A series of four anti-disposed dinuclear platinum(II) complexes featuring metal-metal-to-ligand charge-transfer (MMLCT) excited states, bridged by either 2-hydroxy-6-methylpyridine or 2-hydroxy-6-phenylpyridine and cyclometalated with 7,8-benzoquinoline or 2-phenylpyridine, are presented. The 2-hydroxypyridine bridging ligands control intramolecular d8-d8 metal-metal σ interactions, affecting the frontier orbitals' electronic structure, resulting in marked changes to the ground- and excited-state properties of these complexes. Three of these molecules possess reversible one-electron oxidations in cyclic voltammetry experiments as a result of strong intramolecular metallophilic interactions. In this series of molecules, X-ray crystallography revealed Pt-Pt distances ranging between 2.815 and 2.878 A; the former represents the shortest reported metal-metal distance for platinum(II) dimers possessing low-energy MMLCT transitions. All four molecules reported here display visible absorption bands beyond 500 nm and feature MMLCT-based red photoluminescence (PL) above 700 nm at room temperature with high PL quantum yields (up to 4%) and long excited-state lifetimes (up to 341 ns). The latter were recorded using both transient PL and transient absorption experiments that self-consistently yielded quantitatively identical excited-state lifetimes. The energy-gap law was successfully applied to this series of chromophores, documenting this behavior for the first time in molecules possessing MMLCT excited states. The combined data illustrate that entirely new classes of MMLCT chromophores can be envisioned using bridging pyridyl hydroxides in cooperation with various C^N cyclometalates to achieve photophysical properties suitable for excited-state electron- and energy-transfer chemistry.

Mononuclear metalloenzymes in nature can function in cooperation with precisely positioned redox-active organic cofactors in order to carry out multielectron catalysis. Inspired by the finely tuned redox management of these bioinorganic systems, we present the design, synthesis, and experimental and theoretical characterization of a homologous series of cobalt complexes bearing redox-active pyrazines. These donor moieties are locked into key positions within a pentadentate ligand scaffold in order to evaluate the effects of positioning redox non-innocent ligands on hydrogen evolution catalysis. Both metal- and ligand-centered redox features are observed in organic as well as aqueous solutions over a range of pH values, and comparison with analogs bearing redox-inactive zinc(ii) allows for assignments of ligand-based redox events. Varying the geometric placement of redox non-innocent pyrazine donors on isostructural pentadentate ligand platforms results in marked effects on observed cobalt-catalyzed proton reduction activity. Electrocatalytic hydrogen evolution from weak acids in acetonitrile solution, under diffusion-limited conditions, reveals that the pyrazine donor of axial isomer 1-Co behaves as an unproductive electron sink, resulting in high overpotentials for proton reduction, whereas the equatorial pyrazine isomer complex 2-Co is significantly more active for hydrogen generation at lower voltages. Addition of a second equatorial pyrazine in complex 3-Co further minimizes overpotentials required for catalysis. The equatorial derivative 2-Co is also superior to its axial 1-Co congener for electrocatalytic and visible-light photocatalytic hydrogen generation in biologically relevant, neutral pH aqueous media. Density functional theory calculations (B3LYP-D2) indicate that the first reduction of catalyst isomers 1-Co, 2-Co, and 3-Co is largely metal-centered while the second reduction occurs at pyrazine. Taken together, the data establish that proper positioning of non-innocent pyrazine ligands on a single cobalt center is indeed critical for promoting efficient hydrogen catalysis in aqueous media, akin to optimally positioned redox-active cofactors in metalloenzymes. In a broader sense, these findings highlight the significance of electronic structure considerations in the design of effective electron-hole reservoirs for multielectron transformations.

The need to develop low-cost, sustainable, earth abundant fuel sources is becoming paramount as the rate of global energy consumption continues to increase. Toward this goal, solar energy conversion is an obvious choice, yet the current molecular based technologies still rely heavily on expensive, non-earth abundant photosensitizers, which limits the net benefits of these systems. Complexes of copper(I) have been recognized for decades as viable low-cost, earth abundant alternative photosensitizers in solar energy conversion technologies; however, when used in solution based applications, issues such as geometrical distortions associated with photoexcitation and ligand lability has frustrated numerous research efforts. Fortunately, these investigations have not been in vain, and many investigations have successfully circumvented the aforementioned issues. Recent reports on Cu(I) based photosensitizers demonstrate that they are beginning to rival the performance metrics of the more costly, less earth abundant species typically used in solution-based solar energy conversion schemes. Therefore, this minireview focuses on the most recent and influential advances made in the field of Cu(I) based photosensitizers.

We report four photocatalytically active cobaloxime complexes for light-driven hydrogen evolution. The cobaloxime catalysts are sensitized by different meso-pyridyl boron dipyrromethene (BODIPY) chromophores, bearing either two bromo- or iodo-substituents on the BODIPY core. The pyridine linker between the BODIPY and cobaloxime is further modified by a methyl substituent on the pyridine, influencing the stability and electronic properties of the cobaloxime catalyst and thus the photocatalytic efficiency of each system. Four cobaloxime catalyst complexes and three novel BODIPY chromophores are synthesized and characterized by absorption, fluorescence, infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, and electrochemistry. Crystal structures for the BODIPY-cobaloxime complexes 2 and 3 are presented. In contrast to the photocatalytically inactive, nonhalogenated reference complex 1, the four newly reported molecules are active for photocatalytic hydrogen evolution, with a maximum turnover number (TON) of 30.9 mol equiv of H2 per catalyst for the meso-methylpyridyl 2,6-diiodo BODIPY-sensitized cobaloxime complex 5. We conclude that accessing the photoexcited triplet state of the BODIPY chromophore by introducing heavy atoms (i.e., bromine or iodine) is necessary for efficient electron transfer in this system, enabling catalytic hydrogen generation. In addition, relatively electron-donating pyridyl linkers improve the stability of the complex, increasing the overall TON for hydrogen production.

Homogeneous aqueous solutions of photocatalytic ensembles, consisting of [Ru(bpy)3]2+ as a photosensitizer, ascorbic acid/ascorbate as the electron source, and 10 distinct Co2+-based molecular catalysts, were evaluated for visible-light induced hydrogen evolution using high-throughput screening. The combined results demonstrate that Co2+ complexes bearing tetradentate ligands yield more active photocatalytic compositions than their congeners with pentadentate ligands while operating with high catalyst stability. Additionally, molecular Co2+ catalysts with cis open coordination sites appear to be significantly more active for hydrogen evolution than those with trans open sites. As evidenced by mass spectrometric analysis of the reactor headspace and associated deuteration experiments, the H2 gas generated in all instances was derived from aqueous protons. One of the most promising cis-disposed Co2+ species, [Co(bpyPY2Me)(CH3CN)(CF3SO3)](CF3SO3) (1), engages in highly efficient hydrogen evolving photocatalysis, achieving a turnover number of 4200 (H2/Co) and a turnover frequency of 3200 (H2/Co per h) at pH 4 under simulated sunlight (AM 1.5G, 100 mW cm−2) at room temperature. At equimolar concentrations of photosensitizer and 1, the total hydrogen produced appears to be exclusively limited by the photostability of [Ru(bpy)3]2+, which was observed to decompose into an Ru(bpy)2–ascorbate adduct, as evidenced by HPLC and ESI-MS experiments. Lowering the operating temperature from 27 to 5 °C significantly attenuates bpy dissociation from the sensitizer, resulting in a net ∼two-fold increase in hydrogen production from this composition. The primary electron transfer steps of this photocatalytic ensemble were investigated by nanosecond transient absorption spectroscopy. Photoexcited [Ru(bpy)3]2+ undergoes reductive quenching by ascorbic acid/ascorbate (kq = 2.6 × 107 M−1 s−1), releasing [Ru(bpy)3]+ from the encounter solvent cage with an efficiency of 55 ± 5%. In the presence of catalyst 1, [Ru(bpy)3]+ generated in the initial flash-quench experiment transfers an electron (ket = 2 × 109 M−1 s−1) at an efficiency of 85 ± 10% to the catalyst, which is believed to enter the hydrogen evolution cycle subsequently. Using a combinatorial approach, all ten Co2+ catalysts were evaluated for their potential to operate under neutral pH 7.0 conditions. Catalyst 7, [Co(PY4MeH2)(CH3CN)(CF3SO3)](CF3SO3), was revealed to be most promising, as its performance metrics were only marginally affected by pH and turnover numbers greater than 1000 were easily obtained in photocatalytic hydrogen generation. These comprehensive findings provide guidelines for the development of molecular compositions capable of evolving hydrogen from purely aqueous media.

A series of cyclometalated RuII coordination compounds of the general structural formula [Ru(bpy)2(C∧N)]PF6 {C∧N = 2-phenylpyridine (1), 2-(2,4-difluorophenyl)pyridine (2), 2-(4-methoxyphenyl)-5-methylpyridine (3), benzo[h]quinoline (4); bpy = 2,2′-bipyridine} have been synthesized, structurally and electrochemically characterized, and examined by using a battery of spectroscopic techniques. The combination of static and dynamic photoluminescence at room temperature and 77 K, resonance Raman spectroscopy, cyclic voltammetry, spectroelectrochemistry, and ultrafast transient absorption spectroscopy reveal that – although the nature of the cyclometalating ligand substantially affects the oxidation potential at the metal center – the lowest-energy metal-to-ligand charge-transfer excited state always retains pure Rubpy character across this series of molecules, and the cyclometalating subunit plays the role of ancillary ligand.

An iron complex has been made that has a long-lived excited state and emits light at room temperature as a result of a charge-transfer process. This breakthrough might allow the production of cheap solar cells. See Letter p.695 Transition-metal complexes are used as photosensitizers and photocatalysts, and in light-emitting devices. For these uses, the complexes need to be excited from their ground state to a charge-transfer state, which generally needs to be long-lived to ensure efficient performance. This has made it challenging to replace the scarce but high-performing precious metals used in these complexes with Earth-abundant metals that are cheaper and less toxic. Pavel Chabera et al. now show that a design strategy that utilizes ligands with superior electronic properties yields iron complexes with unprecedented long-lived charge-transfer states. With further development, the approach could deliver iron-based materials for use as light emitters and photosensitizers in solar energy devices.

Degussa P-25 TiO2 bearing surface-anchored Pt(dcbpy)Cl2 [dcbpy = 4,4′-dicarboxylic acid-2,2′-bipyridine] prepared with systematically varied surface coverage produced Pt0 nanoparticles under bandgap illumination in the presence of methanol hole scavengers. Energy-dispersive X-ray spectroscopy confirmed the presence of elemental platinum in the newly formed nanoparticles during scanning transmission electron microscopy (STEM) experiments. According to the statistical analysis of numerous STEM images, the Pt0 nanoclusters were distributed in a segregated manner throughout the titania surface, ranging in size from 1 to 3 nm in diameter. The final achieved nanoparticle size and net hydrogen production were determined as a function of the Pt(dcbpy)Cl2 surface coverage as well as other systematically varied experimental parameters. The hybrid Pt/TiO2 nanomaterials obtained upon complete decomposition of the Pt(dcbpy)Cl2 precursor displayed higher photocatalytic activity (300 μmol/h) for hydrogen evolution in aq...

The goal of this study was to determine whether electrons injected into TiO2 in dye-sensitized solar cells (DSSCs) react with di-iodide, I2•–, a known intermediate in sensitized iodide oxidation. The approach was to utilize time-resolved absorption spectroscopy to quantify the yield of I2•– disproportionation under conditions where I2•– reduction by electrons photoinjected into TiO2, TiO2(e–)s, could be competitive. The DSSC was based on [Ru(dtb)2(dcb)]2+, where dtb is 4,4′-(C(CH3)3)2-2,2′-bipyridine and dcb is 4,4′-(COOH)2-2,2′-bipyridine, sensitized mesoporous nanocrystalline TiO2 thin films sintered onto an optically transparent fluorine-doped tin oxide (FTO) conductive substrate. A transparent Pt counter-electrode and a 0.5 M LiI/0.05 M I2/acetonitrile electrolyte completed the DSSC. After pulsed 532 nm laser excitation, the first iodide oxidation product observed spectroscopically was I2•–. Under all conditions studied, there was no direct evidence for the reaction between TiO2(e–) and I2•–, and the ...

We have developed and optimized a well-controlled and refined methodology for the synthesis of substituted π-conjugated 4,4'-styryl-2,2'-bipyridine ligands and also adapted the tris(heteroleptic) synthetic approach developed by Mann and co-workers to produce two new representative Ru(II)-based complexes bearing the metal oxide surface-anchoring precursor 4,4'-bis[E-(p-methylcarboxy-styryl)]-2,2'-bipyridine. The two targeted Ru(II) complexes, (4,4'-dimethyl-2,2'-bipyridine)(4,4'-di-tert-butyl-2,2'-bipyridine)(4,4'-bis[E-(p-methylcarboxy-styryl)]-2,2'-bipyridine) ruthenium(II) hexafluorophosphate, [Ru(dmbpy)(dtbbpy)(p-COOMe-styryl-bpy)](PF(6))(2) (1) and (4,4'-dimethyl-2,2'-bipyridine)(4,4'-dinonyl-2,2'-bipyridine)(4,4'-bis[E-(p-methylcarboxy-styryl)]-2,2'-bipyridine) ruthenium(II) hexafluorophosphate, [Ru(dmbpy)(dnbpy)(p-COOMe-styryl-bpy)](PF(6))(2) (2) were obtained as analytically pure compounds in high overall yields (50% after 5 steps) and were isolated without significant purification effort. In these tris(heteroleptic) molecules, NMR-based structural characterization became nontrivial as the coordinated ligand sets each sense profoundly distinct magnetic environments greatly complicating traditional 1D spectra. However, rational two-dimensional approaches based on both homo- and heteronuclear couplings were readily applied to these structures producing quite definitive analytical characterization and the associated methodology is described in detail. Preliminary photoluminescence and photochemical characterization of 1 and 2 strongly suggests that both molecules are energetically and kinetically suitable to serve as sensitizers in energy-relevant applications.

The synthesis and photophysics of a new Re(I)-carbonyl diimine complex, Re(PNI-phen)(CO)(3)Cl, where the PNI-phen is N-(1,10-phenanthroline)-4-(1-piperidinyl)naphthalene-1,8-dicarboximide is reported. The metal-to-ligand charge transfer (MLCT) emission lifetime was increased approximately 3000-fold at room temperature with respect to that of the model complex [Re(phen)(CO)(3)Cl] as a result of thermal equilibrium between the emissive (3)MLCT state and a long-lived triplet ligand-centered ((3)LC) state on the PNI chromophore. This represents the longest excited state lifetime (τ = 651 μs) that has ever been observed for a Re(I)-based CT photoluminescence at room temperature. The energy transfer processes and the associated rate constants leading to the establishment of the excited state equilibrium were elucidated by a powerful combination of three techniques (transient visible and infrared (IR) absorption and photoluminescence), each applied from ultrafast to the micro/milliseconds time scale. The MLCT excited state was monitored by transient IR using CO vibrations through time intervals where the corresponding signals obtained in conventional visible transient absorption were completely obscured by overlap with strong transients originating from the pendant PNI chromophore. Following initial excitation of the (1)LC state on the PNI chromophore, energy is transferred to form the MLCT state with a time constant of 45 ps, a value confirmed in all three measurement domains within experimental error. Although transient spectroscopy confirms the production of the (3)MLCT state on ultrafast time scales, Förster resonance energy transfer calculations using the spectral properties of the two chromophores support initial singlet transfer from (1)PNI* to produce the (1)MLCT state by the agreement with the experimentally observed energy transfer time constant and efficiency. Intersystem crossing from the (1)MLCT to the (3)MLCT excited state is believed to be extremely fast and was not resolved with the current experiments. Finally, triplet energy was transferred from the (3)MLCT to the PNI-centered (3)LC state in less than 15 ns, ultimately achieving equilibrium between the two excited states. Subsequent relaxation to the ground state occurred via emission resulting from thermal population of the (3)MLCT state with a resultant lifetime of 651 μs. The title chromophore represents an interesting example of "ping-pong" energy transfer wherein photon excitation first migrates away from the initially prepared (1)PNI* excited state and then ultimately returns to this moiety as a long-lived excited triplet which disposes of its energy by equilibrating with the photoluminescent Re(I) MLCT excited state.

Photon upconversion, the process wherein light of long wavelength is frequency converted to photons of higher energy, is readily achieved at low incident power through sensitized triplet–triplet annihilation (TTA) in various chromophore combinations spanning the UV to the near-IR. This emerging wavelength-shifting technology truly represents a viable route towards converting low energy terrestrial solar photons into light adequate to drive electron transfer in operational photovoltaics. Generalized molecular design constraints, all operational examples reported to date, and measurement techniques applied to these low power nonlinear processes are reviewed in this contribution. In many instances, direct visualization of this phenomenon is presented in solution and within various polymeric host materials.

Here we describe the efficient high yield atmospheric pressure microwave-assisted synthesis for seven distinct RuII coordination complexes relevant to solar energy conversion schemes and dye sensitized solar cells. In all instances, the reaction times have been markedly shortened, concomitant with higher yields with little or no need for subsequent purification and several multi-step reactions proceeded flawlessly in a single pot. Importantly, we observed no evidence for the decarboxylation of the essential metal oxide surface-anchoring 4,4′-diethylester-2,2′-bipyridine or 4,4′-dicarboxy-2,2′-bipyridine ligands as long as open reaction vessel conditions were utilized; these functionalities are not tolerant to sealed microwave reaction (superheated solvent/pressurized) conditions. The combined results suggest that microwave-assisted chemistry is indeed a valuable tool as far as RuII coordination chemistry is concerned and can likely be applied in the combinatorial pursuit of new dyes bearing sensitive functionalities.

Blue-green upconverted emission from 2-chloro-bis-phenylethynylanthracene (2CBPEA) sensitized by the red-absorbing platinum(II)tetraphenyltetrabenzoporphyrin (PtTPBP) has been investigated in N,N-dimethylformamide (DMF). The upconverted singlet fluorescence of 2CBPEA resulting from its sensitized triplet-triplet annihilation (TTA) is observed following selective excitation of PtTPBP at 635 +/- 5 nm. Stern-Volmer analysis of the photoluminescence quenching of PtTPBP by 2CBPEA yields a bimolecular quenching constant of 1.62 x 10(9) M(-1) s(-1), slightly below the diffusion limit in DMF at room temperature. The TTA process was confirmed by the quadratic dependence of the integrated upconverted singlet fluorescence emission profile of 2CBPEA measured as a function of 635 nm incident laser power. Time-resolved emission spectra following 630 nm nanosecond laser pulses illustrate the prompt nature of porphyrin phosphorescence quenching and the delayed nature of the upconverted singlet fluorescence from 2CBPEA. Transient absorption decays monitored at the peak of the characteristic 2CBPEA triplet-triplet excited-state absorption (490 nm) measured as a function of incident nanosecond 630 nm pump laser fluence recovered the rate constant for the sensitized TTA process, k(TT) = 5.64 +/- 0.08 x 10(9) M(-1) s(-1). To calculate this rate constant, we determined the triplet-triplet extinction coefficient of 2CBPEA (12,500 M(-1) cm(-1) at 490 nm) utilizing triplet energy transfer from donors with known excited-state extinction coefficients, namely [Ru(bpy)(3)](2+) and 2-acetonaphthone and averaged these values. The current work, to the best of our knowledge, represents the first example of red-to-blue upconversion thus demonstrating another viable sensitized TTA process, as well as providing the first measurements of k(TT) in a photon upconverting scheme. As 2CBPEA is stable under ambient conditions, this chromophore represents an almost ideal candidate for light-producing sensitized TTA in aerated polymeric materials, and we demonstrate successful translation of the present donor-acceptor/annihilator system into a low T(g) polyurethane.

The photophysical and electrochemical properties of a platinum(II) diimine complex bearing the bidentate diacetylide ligand tolan-2,2'-diacetylide (tda), Pt(dbbpy)(tda) [dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine] (1), are compared with two reference compounds, Pt(dbbpy)(C[triple bond]CPh)(2) (2) and Pt(dppp)tda [dppp = 1,3-bis(diphenylphosphino)propane] (3), respectively. The X-ray crystal structure of 1 is reported, which illustrates the nearly perfect square planarity exhibited by this metallacycle. Chromophore 2 possesses low-lying charge-transfer excited states analogous to 1, whereas structure 3 lacks such excited states but features a low-lying platinum-perturbed tda intraligand triplet manifold. In CH(2)Cl(2), 1 exhibits a broad emission centered at 562 nm at ambient temperature, similar to 2, but with a higher photoluminescence quantum yield and longer excited-state lifetime. In both instances, the photoluminescence is consistent with triplet-charge-transfer excited-state parentage. The rigidity imposed by the cyclic diacetylide ligand in 1 leads to a reduction in nonradiative decay, which enhances its room-temperature photophysical properties. By comparison, 3 radiates highly structured tda-localized triplet-state phosphorescence at room temperature. The 77 K emission spectrum of 1 in 4:1 EtOH/MeOH becomes structured and is quantitatively similar to that measured for 3 under the same conditions. Because the 77 K spectra are nearly identical, the emissions are assigned as (3)tda in nature, implying that the charge-transfer states are raised in energy, relative to the (3)tda levels in 1 in the low-temperature glass. Nanosecond transient absorption spectrometry and ultrafast difference spectra were determined for 1-3 in CH(2)Cl(2) and DMF at ambient temperature. In 1 and 2, the major absorption transients are consistent with the one-electron reduced complexes, corroborated by reductive spectroelectrochemical measurements performed at room temperature. As 3 does not possess any charge-transfer character, excitation into the pipi* transitions of the tda ligand generated transient absorptions in the relaxed excited state assigned to the ligand-localized triplet state. In all three cases, the excited-state lifetimes measured by transient absorption are similar to those measured by time-resolved photoluminescence, suggesting that the same excited states giving rise to the photoluminescence are responsible for the absorption transients. ESR spectroscopy of the anions 1- and 2- and reductive spectroelectrochemistry of 1 and 2 revealed a LUMO based largely on the pi* orbital of the dbbpy ligand. Time-dependent density functional theory calculations performed on 1-3 both in vacuum and in a CH(2)Cl(2) continuum revealed the molecular orbitals, energies, dipole moments, and oscillator strengths for the various electronic transitions in these molecules. A DeltaSCF-method-derived shift applied to the calculated transition energies in the solvent continuum yielded good agreement between theory and experiment for each molecule in this study.

This frontier presentation highlights the historical development of MLCT sensitizers in photochemical upconversion while indentifying current state-of-the-art and exciting opportunities in this arena moving towards the future.

The photophysical properties of mononuclear Pt II chromophores of the general structural formulae: Pt(LL)(C CR) 2 and [Pt(LLL)(C CR)] + (LL = substituted or unsubstituted 2,2′-bipyridine; LLL = substituted or unsubstituted 2,2′:6′,2″-terpyridine; R = aryl or alkyl) are described. Topics related to their preparation, spectroscopy, photochemistry, and photophysics are reviewed.

The Cu(I) metal-to-ligand charge-transfer complex, [Cu(dsbtmp)2](+) (dsbtmp = 2,9-di(sec-butyl)-3,4,7,8-tetramethyl-1,10-phenanthroline), exhibits outstanding stability as a visible-light-absorbing photosensitizer in hydrogen-evolving homogeneous photocatalysis. In concert with the Co(dmgH)2(py)Cl water reduction catalyst and N,N-dimethyl-p-toluidine sacrificial donor in 1:1 H2O:CH3CN, this Cu(I) sensitizer remains active even after 5 days of visible-light-pumped (λex = 452 ± 10 nm) hydrogen evolution catalysis. Deuteration studies illustrate that the hydrogen produced from this composition does indeed originate from aqueous protons.

We describe the synthesis, electrochemistry, and photophysical properties of several Ru(II) complexes bearing different numbers of pyrenylethynylene substituents in either the 5- or 5,5‘-positions of 2,2‘-bipyridine, along with the appropriate Ru(II) model complexes bearing either bromo- or ethynyltoluene functionalities. In addition, we prepared and studied the photophysical behavior of the diimine ligands 5-pyrenylethynylene-2,2‘-bipyridine and 5,5‘-dipyrenylethynylene-2,2‘-bipyridine. Static and dynamic absorption and luminescence measurements reveal the nature of the lowest excited states in each molecule. All model Ru(II) complexes are photoluminescent at room temperature and exhibit excited-state behavior consistent with metal-to-ligand charge transfer (MLCT) characteristics. In the three Ru(II) molecules bearing multiple pyrenylethynylene substituents, there is clear evidence that the lowest excited state is triplet intraligand (3IL)-based, yielding long-lived room temperature phosphorescence in th...

Triplet state photophysics has been generated in two distinct diketopyrrolopyrrole (DPP) chromophores terminated with either phenyl (1) or thienyl (2) spacers, when sandwiched between two Ir(III) complexes using bipyridyl linkers. Upon coordination of the bpy-DPP-bpy subunit resulting in its planarization, the π-conjugation in the DPP chromophore formally extends and was manifested as a substantial red shift in the absorption and fluorescence profiles of 1 and 2. Low energy excitation of these dinuclear metal complexes produced strongly quenched singlet fluorescence, generated quite intense long-lived (τ ∼ 3 μs) absorption transients in the red, sensitized (1)O(2) photoluminescence centered at 1270 nm in aerated solutions, and yielded low temperature near-IR phosphorescence in 1 centered at 950 nm.

The synthesis, structural characterization, and excited-state dynamics of series of diketopyrrolopyrrole (DPP) bridged homodinuclear Ir(III) and heterodinuclear Ir(III)/Pt(II) complexes is described. Steady-state and time-resolved photoluminescence along with transient absorption measurements were used to probe the nature of the emissive and long-lived excited states. Upon excitation into the (1)DPP ligand-localized excited state in the presence of coordinated Ir(III) or Pt(II) metal centers, the intersystem crossing is enhanced, leading to a quenching of the (1)DPP fluorescence and the formation of the long-lived (τ ≈ 30-40 μs) (3)DPP excited state in all instances.

We describe the synthesis, electrochemical, and photophysical properties of two new luminescent Ru(II) diimine complexes covalently attached to one and three 4-piperidinyl-1,8-naphthalimide (PNI) chromophores, [Ru(bpy)(2)(PNI-phen)](PF(6))(2) and [Ru(PNI-phen)(3)](PF(6))(2), respectively. These compounds represent a new class of visible light-harvesting Ru(II) chromophores that exhibit greatly enhanced room-temperature metal-to-ligand charge transfer (MLCT) emission lifetimes as a result of intervening intraligand triplet states ((3)IL) present on the pendant naphthalimide chromophore(s). In both Ru(II) complexes, the intense singlet fluorescence of the pendant PNI chromophore(s) is nearly quantitatively quenched and was found to sensitize the MLCT-based photoluminescence. Excitation into either the (1)IL or (1)MLCT absorption bands results in the formation of both (3)MLCT and (3)IL excited states, conveniently monitored by transient absorption and fluorescence spectroscopy. The relative energy ordering of these triplet states was determined using time-resolved emission spectra at 77 K in an EtOH/MeOH glass where dual emission from both Ru(II) complexes was observed. Here, the shorter-lived higher energy emission has a spectral profile consistent with that typically observed from (3)MLCT excited states, whereas the millisecond lifetime lower energy band was attributed to (3)IL phosphorescence of the PNI chromophore. At room temperature the data are consistent with an excited-state equilibrium between the higher energy (3)MLCT states and the lower energy (3)PNI states. Both complexes display MLCT-based emission with room-temperature lifetimes that range from 16 to 115 micros depending upon solvent and the number of PNI chromophores present. At 77 K it is apparent that the two triplet states are no longer in thermal equilibrium and independently decay to the ground state.

Room temperature (RT) phosphorescence is observed from a naphthalimide species for the first time in the square-planar chromophore Pt(dbbpy)(C[triple bond]C-NI)(2), where NI = N-butyl-4-ethynylnaphthalimide and dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine. The combination of static and time-resolved absorption and photoluminescence data is uniformly consistent with triplet-state photophysics localized on an appended C[triple bond]C-NI unit following excitation into the low-energy absorption bands. This molecule features rather impressive long-lifetime, high-quantum-efficiency NI-based RT phosphorescence (tau = 124 micros; Phi = 0.215) centered at 621 nm, exemplifying how the platinum acetylide linkage strongly promotes intersystem crossing in the NI subunit, representative of a class of molecules whose excited states are typically dominated by singlet fluorescence.

Electron and energy transfer processes from CuI MLCT excited states are reviewed. New results demonstrate clearly that these excited states undergo oxidative electron transfer quenching and energy transfer processes. The yields and dynamics of these processes have been spectroscopically quantified. Interfacial electron transfer from CuI MLCT excited states to wide band gap semiconductors has been observed. When utilized in photoelectrochemical cells, this interfacial electron transfer process provides a means for the conversion of light directly into electrical power.

Nanosecond step-scan Fourier transform infrared spectroscopy permits the observation of triplet intraligand ((3)IL) character in the excited states of [Ru(bpy)2(PNI-phen)]2+ and [Ru(PNI-phen)3]2+ where PNI is 4-piperidinyl-1,8-naphthalimide. After pulsed 355-nm laser excitation, the two ground-state imide C=O bands in each compound are bleached and two substantially lower energy vibrations are produced; the lower energy feature appears as two distinct bands split by an overlapping transient bleach. Model studies confirm that the time-resolved vibrational data are consistent with photoinduced sensitization of the 3IL excited state. Density functional theory calculations also support these assignments because localization of triplet electron density on the PNI moiety is expected to lead to red-shifted C=O vibrations of magnitude similar to those measured experimentally. The current results illustrate that triplet electron density can be directly tracked by time-resolved infrared measurements in metal-organic chromophores and that frequency shifts comparable to those observed in charge-transfer systems can be realized.

Electronic structure and photophysical properties have been investigated for a new series of fluorinated iridium complexes with the parent [Ir(ppy)2(deeb)](PF6) (deeb is 4,4'-diethylester-2,2'-bipyridine). Time resolved infrared spectroscopy (TRIR) has been used to observe the long-lived triplet excited state of each complex confirming its mixed charge transfer character. Supplementary evidence of charge transfer in the triplet state is provided via emission spectroscopy, transient absorption spectroscopy, and density functional theory (DFT) calculations. Both computational and spectroscopic assignments reveal consistency in the first excitation throughout the series of complexes. Electrochemical measurements meanwhile show that increasing fluorination still induces expected shifting of frontier orbitals. Excited states beyond the lowest lying triplet are probed for the complexes via UV-vis spectroscopy which reveals three distinct features. These features are assigned via time-dependent DFT (TD-DFT) to build a broader understanding of electronic structure.

We present the synthesis, photophysical characterization, and electrochemistry of three series of cyclometalated binuclear platinum(II) complexes, each bridged by two 3,5-disubstituted pyrazolate ligands (μ-R2pz). These neutral compounds have the general formula [C∧NPt(μ-R2pz)]2, where C∧N is a cyclometalating ligand corresponding to 2-(2′-thienyl)pyridine (thpy), 1-phenylisoquinoline (piq), or 7,8-benzoquinoline (bzq) with R = H, Me, iPr, Ph, corresponding to series I–III dimers, respectively. Systematic variation of the cyclometalating ligands in addition to the bridging pyrazolates renders colorful structures exhibiting a range of electrochemical and spectroscopic behavior with absorption and photoluminescence properties tuned over a wide portion of the visible spectrum. Steric bulk introduced into the 3,5-positions on the pz bridges readily modulates intramolecular d8–d8 metal–metal σ interactions strongly affecting the frontier orbitals’ electronic structure, manifested by changes in absorption and e...

Electron and energy transfer from copper 1,10-phenanthroline excited states is observed at room temperature in organic solvents. The copper phenanthroline excited states are metal-to-ligand charge-transfer in nature and have lifetimes of approximately 70-250 ns in dichloromethane solution if methyl or phenyl substituents are placed in the 2- and 9-positions of the phenanthroline ligand. The unsubstituted cuprous compound Cu(phen)(2)(PF(6)) is nonemissive under these conditions, and the excited state lifetime is

Room temperature phosphorescence has been observed in a synthetically facile Pt(II) complex, Pt(dbbpy)(CtriplebondC-pyrene)(2) (dbbpy = 4,4'-di(tert-butyl)-2,2'-bipyridine; CtriplebondC-pyrene = 1-ethynylpyrene), in fluid solution. The static and time-resolved absorption and luminescence data are consistent with phosphorescence emerging from the appended CtriplebondC-pyrenyl units following excitation into the low energy dpi Pt --pi* dbbpy metal-to-ligand charge transfer absorption bands.

The 9-anthryltriphenylstibonium cation, [1](+), has been synthesized and used as a sensor for the toxic fluoride anion in water. This stibonium cation complexes fluoride ions to afford the corresponding fluorostiborane 1-F. This reaction, which occurs at fluoride concentrations in the parts per million range, is accompanied by a drastic fluorescence turn-on response. It is also highly selective and can be used in plain tap water or bottled water to test fluoridation levels.

The synthesis, electrochemistry, and photophysical behavior of a Pt(II) terpyridyl perylenediimide (PDI) acetylide (1) charge-transfer complex is reported. The title compound exhibits strong (ε ≈ 5 × 10(4) M(-1)cm(-1)) low-energy PDI acetylide-based π-π* absorption bands in the visible range extending to 600 nm, producing highly quenched singlet fluorescence (Φ = 0.014 ± 0.001, τ = 109 ps) with respect to a nonmetalated PDI model chromophore. Nanosecond transient absorption spectroscopy revealed the presence of a long excited-state lifetime (372 ns in 2-methyltetrahydrofuran) with transient features consistent with the PDI-acetylide triplet state, ascertained by direct comparison to a model Pt(II) PDI-acetylide complex lacking low-energy charge-transfer transitions. For the first time, time-resolved step-scan FT-IR spectroscopy was used to characterize the triplet excited state of the PDI-acetylide sensitized in the title compound and its associated model complex. The observed red shifts (∼30-50 cm(-1)) in the C═O and C≡C vibrations of the two Pt(II) complexes in the long-lived excited state are consistent with formation of the (3)PDI acetylide state and found to be in excellent agreement with the expected change in the relevant DFT-calculated IR frequencies in the nonmetalated PDI model chromophore (ground singlet state and lowest triplet excited state). Formation of the PDI triplet excited state in the title chromophore was also supported by sensitization of the singlet oxygen photoluminescence centered at ∼1275 nm in air-saturated acetonitrile solution, Φ((1)O(2)) = 0.52. In terms of light emission, only residual PDI-based red fluorescence could be detected and no corresponding PDI-based phosphorescence was observed in the visible or NIR region at 298 or 77 K in the Pt(II) terpyridyl perylenediimideacetylide.