Multimodular Wide-Band Capturing Nanohybrids: Role of Carbon Nanotubes in Slowing Charge Recombination in Supramolecular C60-BisstyrylBODIPY-(Zinc Porphyrin)2 Donor-Acceptor Molecular Cleft.

The importance of diameter-sorted single-wall carbon nanotubes (SWCNTs) noncovalently bound to a donor-acceptor molecular cleft, 1, in prolonging the lifetime of charge-separated states is successfully demonstrated. For this, using a multistep synthetic procedure, a wide-band capturing, multimodular, C60-bisstyrylBODIPY-(zinc porphyrin)2, molecular cleft 1, was newly synthesized and shown to bind diameter-sorted SWCNTs. The molecular cleft and its supramolecular assemblies were characterized by a suite of physicochemical techniques. Free-energy calculations suggested that both the (6,5) and (7,6) SWCNTs bound to 1 act as hole acceptors during the photoinduced sequential electron transfer events. Consequently, selective excitation of 1 in 1:SWCNT hybrids revealed a two-step electron transfer, leading to the formation of charge-separated states. Due to the distant separation of the cation and anion radical species within the supramolecules, improved lifetimes of the charge-separated states could be achieved. The present supramolecular strategy of improving charge separation involving SWCNTs and donor-acceptor molecular clefts highlights the potential application of these hybrid materials for various light energy harvesting and optoelectronic applications.

Intramolecular Charge Transfer and Spin-Orbit Coupled Intersystem Crossing in Hypervalent Phosphorus(V) and Antimony(V) Porphyrin Black Dyes.

Porphyrin dyes with strong push-pull type intramolecular charge transfer (ICT) character and broad absorption across the visible spectrum are reported. This combination of properties has been achieved by functionalizing the periphery of hypervalent and highly electron-deficient phosphorus(V) and antimony(V) centered porphyrins with electron-rich triphenylamine (TPA) groups. As a result of the large difference in electronegativity between the porphyrin ring and the peripheral groups, their absorption profiles show several strong charge transfer transitions, which in addition to the porphyrin-centered π → π* transitions, make them panchromatic black dyes with high absorption coefficients between 200 and 800 nm. Time-resolved optical and electron paramagnetic resonance (EPR) studies show that the lowest triplet state also has ICT character and is populated by spin-orbit coupled intersystem crossing.

Novel Benzothiadiazole-based Donor-Acceptor Systems: Synthesis, Ultrafast Charge Transfer and Separation Dynamics.

Near-infrared (NIR) absorbing electron donor-acceptor (D-A) chromophores have been at the forefront of current energy research owing to their facile charge transfer (CT) characteristics, which are primitive for photovoltaic applications. Herein, we have designed and developed a new set of benzothiadiazole (BTD)-based tetracyanobutadiene (TCBD)/dicyanoquinodimethane (DCNQ)-embedded multimodular D-A systems (BTD1-BTD6) and investigated their inherent photo-electro-chemical responses for the first time having identical and mixed terminal donors of variable donicity. Apart from poor luminescence, the appearance of broad low-lying optical transitions extendable even in the NIR region (>1000 nm), particularly in the presence of the auxiliary acceptors, are indicative of underlying nonradiative excited state processes leading to robust intramolecular CT and subsequent charge separation (CS) processes in these D-A constructs. While electrochemical studies identify the moieties involved in these photo-events, orbital delocalization and consequent evidence for the low-energy CT transitions have been achieved from theoretical calculations. Finally, the spectral and temporal responses of different photoproducts are obtained from femtosecond transient absorption studies, which, coupled with spectroelectrochemical data, identify broad NIR signals as CS states of the compounds. All the systems are found to be susceptible to ultrafast (~ps) CT and CS before carrier recombination to the ground state, which is, however, significantly facilitated after incorporation of the secondary TCBD/DCNQ acceptors, leading to faster and thus efficient CT processes, particularly in polar solvents. These findings, including facile CT/CS and broad and intense panchromatic absorption over a wide window of the electromagnetic spectrum, are likely to expand the horizons of BTD-based multimodular CT systems to revolutionize the realm of solar energy conversion and associated photonic applications.

Near-IR Capturing N-Methylbenzene Sulfonamide-Phenothiazine Incorporating Strong Electron Acceptor Push-Pull Systems: Photochemical Ultrafast Carrier Dynamics.

Unraveling the intriguing aspects of the intramolecular charge transfer (ICT) phenomenon of multi-modular donor-acceptor-based push-pull systems are of paramount importance considering their promising applications, particularly in solar energy harvesting and light-emitting devices. Herein, a series of symmetrical and unsymmetrical donor-acceptor chromophores 1-6, are designed and synthesized by the Corey-Fuchs reaction via Evano's condition followed by [2+2] cycloaddition retroelectrocyclic ring-opening reaction with strong electron acceptors TCNE and TCNQ in good yields (~60-85 %). The photophysical, electrochemical, and computational studies are investigated to explore the effect of incorporation of strong electron acceptors 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and dicyanoquinodimethane (DCNQ) with phenothiazine (PTZ) donor. An additional low-lying broad absorption band extended towards the near-infrared (NIR) region suggests charge polarization after the introduction of the electron acceptors in both symmetrical and asymmetrical systems, leading to such strong ICT bands. The electrochemical properties reveal that reduction potentials of 3 and 6 are lower than those of 2 and 5, suggesting DCNQ imparts more on the electronic properties and hence largely contributes to the stabilization of LUMO energy levels than TCBD, in line with theoretical observations. Relative positions of the frontier orbitals on geometry-optimized structures further support accessing donor-acceptor sites responsible for the ICT transitions. Eventually, ultrafast carrier dynamics of the photoinduced species are investigated by femtosecond transient absorption studies to identify their spectral characteristics and target analysis further provides information about different excited states photophysical events including ICT and their associated time profiles. The key findings obtained here related to excited state dynamical processes of these newly synthesized systems are believed to be significant in advancing their prospect of utilization in solar energy conversion and related photonic applications.

Electrocatalytic Dinitrogen Reduction to Ammonia Using Easily Reducible N-Fused Cobalt Porphyrins.

Single-site molecular electrocatalysts, especially those that perform catalytic conversion of N2 to NH3 under mild conditions, are highly desirable to derive fundamental structure-activity relations and as potential alternatives to the current energy-consuming Haber-Bosch ammonia production process. Combining theoretical calculations with experimental evidence, it has been shown that easily reducible cobalt porphyrins catalyze the six-electron, six-proton reduction of dinitrogen to NH3 at neutral pH and under ambient conditions. Two easily reducible N-fused cobalt porphyrins - CoNHF and CoNHF(Br)2 - reveal NRR activity with Faradic efficiencies between 6-7.5 % with ammonia yield rates of 300-340 µmol g-1 h-1. Contrary to this, much harder-to-reduce N-fused porphyrins - CoNHF(Ph)2 and CoNHF(PE)2 - reveal no NRR activity. The present study highlights the significance of tuning the redox and structural properties of single-site NRR electrocatalysts for improved NRR activity under mild conditions.

Photoinduced Energy and Electron Transfer in a 'Two-Point' Bound Panchromatic, Near-Infrared-Absorbing Bis-styrylBODIPY(Zinc Porphyrin)2 - Fullerene Self-Assembled Supramolecular Conjugate.

Structurally well-defined self-assembled supramolecular multi-modular donor-acceptor conjugates play a significant role in furthering our understanding of photoinduced energy and electron transfer events occurring in nature, e. g., in the antenna-reaction centers of photosynthesis and their applications in light energy harvesting. However, building such multi-modular systems capable of mimicking the early events of photosynthesis has been synthetically challenging, causing a major hurdle for its growth. Often, multi-modularity is brought in by combining both covalent and noncovalent approaches. In the present study, we have developed such an approach wherein a π-extended conjugated molecular cleft, two zinc(II)porphyrin bearing bisstyrylBODIPY (dyad, 1), has been synthesized. The binding of 1 via a 'two-point' metal-ligand coordination of a bis-pyridyl fulleropyrrolidine (2), forming a stable self-assembled supramolecular complex (1 : 2), has been established. The self-assembled supramolecular complex has been fully characterized by a suite of physico-chemical methods, including TD-DFT studies. From the established energy diagram, both energy and electron transfer events were envisioned. In dyad 1, selective excitation of zinc(II)porphyrin leads to efficient singlet-singlet excitation transfer to (bisstyrly)BODIPY with an energy transfer rate constant, kEnT of 2.56×1012 s-1. In complex 1 : 2, photoexcitation of zinc(II)porphyrin results in ultrafast photoinduced electron transfer with a charge separation rate constant, kCS of 2.83×1011 s-1, and a charge recombination rate constant, kCR of 2.51×109 s-1. For excitation at 730 nm corresponding to bisstyrylBODIPY, similar results are obtained, where a biexponential decay yielded estimated values of kCS 3.44×1011 s-1 and 2.97×1010 s-1, and a kCR value of 2.10×1010 s-1. The newly built self-assembled supramolecular complex has been shown to successfully mimic the early events of the photosynthetic antenna-reaction center events.

Excited Charge Separation in a π-Interacting Phenothiazine-Zinc Porphyrin-Fullerene Donor-Acceptor Conjugate.

We have designed, synthesized, and characterized a donor-acceptor triad, SPS-PPY-C60, that consists of a π-interacting phenothiazine-linked porphyrin as a donor and sensitizer and fullerene as an acceptor to seek charge separation upon photoexcitation. The optical absorption spectrum revealed red-shifted Soret and Q-bands of porphyrin due to charge transfer-type interactions involving the two ethynyl bridges carrying electron-rich and electron-poor substituents. The redox properties suggested that the phenothiazine-porphyrin part of the molecule is easier to oxidize and the fullerene part is easier to reduce. DFT calculations supported the redox properties wherein the electron density of the highest molecular orbital (HOMO) was distributed over the donor phenothiazine-porphyrin entity while the lowest unoccupied molecular orbital (LUMO) was distributed over the fullerene acceptor. TD-DFT studies suggested the involvement of both the S2 and S1 states in the charge transfer process. The steady-state emission spectrum, when excited either at porphyrin Soret or visible band absorption maxima, revealed quenched emission both in nonpolar and polar solvents, suggesting the occurrence of excited state events. Finally, femtosecond transient absorption spectral studies were performed to witness the charge separation by utilizing solvents of different polarities. The transient data was further analyzed by GloTarAn by fitting the data with appropriate models to describe photochemical events. From this, the average lifetime of the charge-separated state calculated was found to be 169 ps in benzonitrile, 319 ps in dichlorobenzene, 1.7 ns in toluene for Soret band excitation, and ∼320 ps for Q-band excitation in benzonitrile.

Far-Red Excitation Induced Electron Transfer in Bis Donor-AzaBODIPY Push-Pull Systems; Role of Nitrogenous Donors in Promoting Charge Separation.

A far-red absorbing sensitizer, BF2 -chelated azadipyrromethane (azaBODIPY) has been employed as an electron acceptor to synthesize a series of push-pull systems linked with different nitrogenous electron donors, viz., N,N-dimethylaniline (NND), triphenylamine (TPA), and phenothiazine (PTZ) via an acetylene linker. The structural integrity of the newly synthesized push-pull systems was established by spectroscopic, electrochemical, spectroelectrochemical, and DFT computational methods. Cyclic and differential pulse voltammetry studies revealed different redox states and helped in the estimation of the energies of the charge-separated states. Further, spectroelectrochemical studies performed in a thin-layer optical cell revealed diagnostic peaks of azaBODIPY⋅- in the visible and near-IR regions. Free-energy calculations revealed the charge separation from one of the covalently linked donors to the 1 azaBODIPY* to yield Donor⋅+ -azaBODIPY⋅- to be energetically favorable in a polar solvent, benzonitrile, and the frontier orbitals generated on the optimized structures helped in assessing such a conclusion. Consequently, the steady-state emission studies revealed quenching of the azaBODIPY fluorescence in all of the investigated push-pull systems in benzonitrile and to a lesser extent in mildly polar dichlorobenzene, and nonpolar toluene. The femtosecond pump-probe studies revealed the occurrence of excited charge transfer (CT) in nonpolar toluene while a complete charge separation (CS) for all three push-pull systems in polar benzonitrile. The CT/CS products populated the low-lying 3 azaBODIPY* prior to returning to the ground state. Global target (GloTarAn) analysis of the transient data revealed the lifetime of the final charge-separated states (CSS) to be 195 ps for NND-derived, 50 ps for TPA-derived, and 85 ps for PTZ-derived push-pull systems in benzonitrile.

Assembling Artificial Photosynthetic Models in Water Using ß-Cyclodextrin-Conjugated Phthalocyanines as Building Blocks.

Two water-soluble zinc(II) phthalocyanines substituted with two or four permethylated ß-cyclodextrin (ß-CD) moieties at the α positions have been utilized as building blocks for the construction of artificial photosynthetic models in water. The hydrophilic and bulky ß-CD moieties not only can increase the water solubility of the phthalocyanine core and prevent its stacking in water but can also bind with a tetrasulfonated zinc(II) porphyrin (ZnTPPS) and/or sodium 2-anthraquinonesulfonate (AQ) in water through host-guest interactions. The binding interactions of these species have been studied spectroscopically, while the photoinduced processes of the resulting complexes have been investigated using steady-state and time-resolved spectroscopic methods. In the ternary complexes, the ZnTPPS units serve as light-harvesting antennas to capture the light energy and transfer it to the phthalocyanine core via efficient excitation energy transfer. The excited phthalocyanine is subsequently quenched by the electron-deficient AQ units through electron transfer. Femtosecond transient absorption spectroscopy provides clear evidence for the singlet-singlet energy transfer from the photo-excited ZnTPPS to the phthalocyanine core with a rate constant (kENT ) in the order of 109  s-1 . The population of phthalocyanine radical cations indicates the occurrence of electron transfer from the excited phthalocyanine to the AQ moieties, forming a charge-separated state.

Zinc Tetrapyrrole Coordinated to Imidazole Functionalized Tetracyanobutadiene or Cyclohexa-2,5-diene-1,4-diylidene-expanded-tetracyanobutadiene Conjugates: Dark vs. Light-Induced Electron Transfer.

Using the popular metal-ligand axial coordination self-assembly approach, donor-acceptor conjugates have been constructed using zinc tetrapyrroles (porphyrin (ZnP), phthalocyanine (ZnPc), and naphthalocyanine (ZnNc)) as electron donors and imidazole functionalized tetracyanobutadiene (Im-TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded-tetracyanobutadiene (Im-DCNQ) as electron acceptors. The newly formed donor-acceptor conjugates were fully characterized by a suite of physicochemical methods, including absorption and emission, electrochemistry, and computational methods. The measured binding constants for the 1 : 1 complexes were in the order of 104 -105  M-1 in o-dichlorobenzene. Free-energy calculations and the energy level diagrams revealed the high exergonicity for the excited state electron transfer reactions. However, in the case of the ZnNc:Im-DCNQ complex, owing to the facile oxidation of ZnNc and facile reduction of Im-DCNQ, slow electron transfer was witnessed in the dark without the aid of light. Systematic transient pump-probe studies were performed to secure evidence of excited state charge separation and gather their kinetic parameters. The rate of charge separation was as high as 1011  s-1 suggesting efficient processes. These findings show that the present self-assembly approach could be utilized to build donor-acceptor constructs with powerful electron acceptors, TCBD and DCNQ, to witness ground and excited state charge transfer, fundamental events required in energy harvesting, and building optoelectronic devices.

Symmetrically Functionalized Copper and Silver Corrole-Bis-Tetracyanobutadiene Push-Pull Conjugates: Efficient Population of Triplet States via Charge Transfer.

Copper and silver tritolylcorroles (TTC) are symmetrically functionalized to carry two tetracyanobutadiene (TCBD) entities via [2+2] cycloaddition-retroeletrocyclization reaction involving ethynyl functionalized corroles with an electron acceptor, tetracyanoethylene (TCNE) in excellent yields, as the first examples of corrole-TCBD push-pull systems. The strong push-pull effect resulted in charge polarization in the ground state resulting in a considerable hypsochromic shift of the spectrum extending it into the near-IR region. Electrochemical studies coupled with computational studies revealed considerable interactions between the two TCBD entities via the corrole π-system and the degree of such interactions was found to depend on the metal ion present in the corrole cavity. Energy considerations suggested charge transfer (CT) from the S2 or vibrationally hot S1 state but not the relaxed S1 state in the case of CuTTC(TCBD)2 while CT to occur from all these states in the case of AgTTC(TCBD)2 . Additionally, the high-energy CT states populate the low-lying triplet states. Systematic femtosecond pump-probe studies provided the ultimate proof for the occurrence of excited CT as a function of excitation wavelength followed by the efficient population of the triplet states. The present study brings out the significance of charge transfer in efficiently populating the triplet states in rather unusual copper and silver corroles carrying two TCBD entities.

Panchromatic Light-Capturing Bis-styryl BODIPY-Perylenediimide Donor-Acceptor Constructs: Occurrence of Sequential Energy Transfer Followed by Electron Transfer.

Two wide-band-capturing donor-acceptor conjugates featuring bis-styrylBODIPY and perylenediimide (PDI) have been newly synthesized, and the occurrence of ultrafast excitation transfer from the 1 PDI* to BODIPY, and a subsequent electron transfer from the 1 BODIPY* to PDI have been demonstrated. Optical absorption studies revealed panchromatic light capture but offered no evidence of ground-state interactions between the donor and acceptor entities. Steady-state fluorescence and excitation spectral recordings provided evidence of singlet-singlet energy transfer in these dyads, and quenched fluorescence of bis-styrylBODIPY emission in the dyads suggested additional photo-events. The facile oxidation of bis-styrylBODIPY and facile reduction of PDI, establishing their relative roles of electron donor and acceptor, were borne out by electrochemical studies. The electrostatic potential surfaces of the S1 and S2 states, derived from time-dependent DFT calculations, supported excited charge transfer in these dyads. Spectro-electrochemical studies on one-electron-oxidized and one-electron-reduced dyads and the monomeric precursor compounds were also performed in a thin-layer optical cell under corresponding applied potentials. From this study, both bis-styrylBODIPY⋅+ and PDI⋅- could be spectrally characterizes and were subsequently used in characterizing the electron-transfer products. Finally, pump-probe spectral studies were performed in dichlorobenzene under selective PDI and bis-styrylBODIPY excitation to secure energy and electron-transfer evidence. The measured rate constants for energy transfer, kENT , were in the range of 1011  s-1 , while the electron transfer rate constants, kET , were in the range of 1010  s-1 , thus highlighting their potential use in solar energy harvesting and optoelectronic applications.

Naphthodithiophene-Fused Porphyrins: Synthesis, Characterization, and Impact of Extended Conjugation on Aromaticity.

The fusion of tetrapyrroles with aromatic heterocycles constitutes a useful tool for manipulating their opto-electronic properties. In this work, the synthesis of naphthodithiophene-fused porphyrins was achieved through a Heck reaction-based cascade of steps followed by the Scholl reaction. The naphthodithiophene-fused porphyrins display a unique set of optical and electronic properties. Fusion of the naphtho[2,1-b:3,4-b']dithiophene to porphyrin (F2VTP) leads to a ~20% increase in the fluorescence lifetime, which is accompanied, unexpectedly, by a more than two-fold drop in the emission quantum yield (ϕ=0.018). In contrast, fusion of the isomeric naphtho[1,2-b:4,3-b']dithiophene to porphyrin (F3VPT) results in a ~1.5-fold increase in the fluorescence quantum yield (ϕ=0.13) with a concomitant ~30 % increase in the fluorescence lifetime. This behavior suggests that fusion of the porphyrin with the naphthodithiopheno-system mainly affects the radiative rate constant in the Q-state deactivation pathway, where the effects of the isomeric naphtho[2,1-b:3,4-b']dithiophene- versus naphtho[1,2-b:4,3-b']dithiophene-fusion are essentially the opposite. Interestingly, nucleus-independent chemical shifts analysis revealed a considerable difference between the aromaticities of these two isomeric systems. Our results demonstrate that subtle structural differences in the fused components of the porphyrin can be reflected in rather significant differences between the photophysical properties of the resulting systems.

Panchromatic Light-Capturing Bis-styryl BODIPY-Perylenediimide Donor-Acceptor Constructs: Occurrence of Sequential Energy Transfer Followed by Electron Transfer.

Invited for the cover of this issue are the groups of Fernando Fernández-Lázaro and Ángela Sastre-Santos at the Universidad Miguel Hernández, Elche, Spain, and Francis D'Souza at the University of North Texas at Denton, Texas, USA. The image depicts the structure and properties of bis-styryl BODIPY-perylenediimide donor-acceptor constructs. Read the full text of the article at 10.1002/chem.202301686.

Fluorinated Antimony(V) Tetraarylporphyrins as High-Valent Electron Acceptors with Unparalleled Reduction Potentials.

A series of fluorinated antimony(V) porphyrins, SbTPP(OMe)2·PF6, SbTPP(OTFE)2·PF6, SbT(4F)PP(OMe)2·PF6, SbT(35F)PP(OMe)2·PF6, SbT(345F)PP(OMe)2·PF6, SbT(4CF3)PP(OMe)2·PF6, SbT(35CF3)PP(OMe)2·PF6, and SbT(35CF3)PP(OTFE)2·PF6, have been synthesized with phenyl [P], 4-fluorophenyl [(4F)P], 3,5-difluorophenyl [(35F)P], 3,4,5-difluorophenyl [(345F)P], 4-trifluoromethylphenyl [(4CF3)P], and 3,5-bis(trifluoromethyl)phenyl [(35CF3)P], in the meso-positions. Additionally, the SbTPP(OTFE)2·PF6 and SbT(35CF3)PP(OTFE)2·PF6 carry trifluoroethoxy units in their axial-positions. The fluorination on the porphyrin peripherals ranges from zero fluorine atoms in SbTPP(OMe)2·PF6 to 30 fluorine atoms in SbT(35CF3)PP(OTFE)2·PF6. X-ray crystallography confirmed the structures of the investigated antimony(V) porphyrins. The absorption spectra depend on the number of fluorine atoms as it is blue-shifted with increasing fluorination. The series also exhibited rich redox chemistry with two reduction processes and one oxidation process. Remarkably, these porphyrins manifested the lowest reduction potentials reported among the main-group porphyrins, which are as low as -0.08 V vs SCE for SbT(35CF3)PP(OTFE)2·PF6. On the contrary, the oxidation potentials were found to be very large, that is equal to 2.20 V vs SCE or even higher for SbT(4CF3)PP(OMe)2·PF6 or SbT(35CF3)PP(OMe)2·PF6 and SbT(35CF3)PP(OTFE)2·PF6, respectively. These unprecedented potentials are due to a combination of two factors: (i) the +5-oxidation state of antimony in the porphyrin cavity and (ii) the presence of the strong electron-withdrawing fluorine atoms on the porphyrin peripherals. Density functional theory (DFT) calculations were used to support the experimental results. The systematic study of antimony(V) porphyrins, especially their high potentials, make them ideal for the construction of photoelectrodes and excellent electron acceptors for photoelectrochemical cells and artificial photosynthetic systems, respectively, for solar energy conversion and storage applications.

Emissive Substoichiometric Covalent Organic Frameworks for Water Sensing and Harvesting.

Emissive covalent organic frameworks (COFs) have recently emerged as next-generation porous materials with attractive properties such as tunable topology, porosity, and inherent photoluminescence. Among the different types of COFs, substoichiometric frameworks (so-called Type III COFs) are especially attractive due to the possibility of not only generating unusual topology and complex pore architectures but also facilitating the introduction of well-defined functional groups at precise locations for desired functions. Herein, the first example of a highly emissive (PLQY 6.8%) substoichiometric 2D-COF (COF-SMU-1) featuring free uncondensed aldehyde groups is reported. In particular, COF-SMU-1 features a dual-pore architecture with an overall bex net topology, tunable emission in various organic solvents, and distinct colorimetric changes in the presence of water. To gain further insights into its photoluminescence properties, the charge transfer, excimer emission, and excited state exciton dynamics of COF-SMU-1 are investigated using femtosecond transient absorption spectroscopy in different organic solvents. Additionally, highly enhanced atmospheric water-harvesting properties of COF-SMU-1 are revealed using FT-IR and water sorption studies.The findings will not only lead to in-depth understanding of structure-property relationships in emissive COFs but also open new opportunities for designing COFs for potential applications in solid-state lighting and water harvesting.

Stability and activity of titanium oxynitride thin films for the electrocatalytic reduction of nitrogen to ammonia at different pH values.

The production of ammonia for agricultural and energy demands has accelerated research for more environmentally-friendly synthesis options, particularly the electrocatalytic reduction of molecular nitrogen (nitrogen reduction reaction, NRR). Catalyst activity for NRR, and selectivity for NRR over the competitive hydrogen evolution reaction (HER), are critical issues for which fundamental knowledge remains scarce. Herein, we present results regarding the NRR activity and selectivity of sputter-deposited titanium nitride and titanium oxynitride films for NRR and HER. Electrochemical, fluorescence and UV absorption measurements show that titanium oxynitride exhibits NRR activity under acidic conditions (pH 1.6, 3.2) but is inactive at pH 7. Ti oxynitride is HER inactive at all these pH values. In contrast, TiN - with no oxygen content upon deposition - is both NRR and HER inactive at all the above pH values. This difference in oxynitride/nitride reactivity is observed despite the fact that both films exhibit very similar surface chemical compositions - predominantly TiIV oxide - upon exposure to ambient, as determined by ex situ X-ray photoelectron spectroscopy (XPS). XPS, with in situ transfer between electrochemical and UHV environments, however, demonstrates that this TiIV oxide top layer is unstable under acidic conditions, but stable at pH 7, explaining the inactivity of titanium oxynitride at this pH. The inactivity of TiN at acidic and neutral pH is explained by DFT-based calculations showing that N2 adsorption at N-ligated Ti centers is energetically significantly less favorable than at O-ligated centers. These calculations also predict that N2 will not bind to TiIV centers due to a lack of π-backbonding. Ex situ XPS measurements and electrochemical probe measurements at pH 3.2 demonstrate that Ti oxynitride films undergo gradual dissolution under NRR conditions. The present results demonstrate that the long-term catalyst stability and maintenance of metal cations in intermediate oxidation states for pi-backbonding are critical issues worthy of further examination.

ß-Pyrrole Functionalized Push or Pull Porphyrins: Excited Charge Transfer Promoted Singlet Oxygen Generation.

Singlet oxygen (1O2) producing photosensitizers are highly sought for developing new photodynamic therapy agents and facilitating 1O2-involved chemical reactions. Often singlet oxygen is produced by the reaction of triplet-excited photosensitizers with dioxygen via an energy transfer mechanism. In the present study, we demonstrate a charge transfer mechanism to produce singlet oxygen involving push or pull functionalized porphyrins. For this, 20 ß-pyrrole functionalized porphyrins carrying either an electron-rich push or electron-deficient pull group have been newly synthesized. Photoexcitation of these push-pull porphyrins has been shown to produce high-energy MPδ+-Aδ- or MPδ--Dδ+ charge transfer states. Subsequent charge recombination results in populating the triplet excited states of extended lifetimes in the case of the push group containing porphyrins that eventually react with dioxygen to produce the reactive singlet oxygen of relatively higher quantum yields. The effect of the push and pull groups on the porphyrin periphery in governing initial charge transfer, the population of triplet excited states and their lifetimes, and resulting in improved singlet oxygen quantum yields are systematically probed. The improved performance of 1O2 generation by porphyrins carrying push groups is borne out from this study.

Accelerated Intramolecular Charge Transfer in Tetracyanobutadiene- and Expanded Tetracyanobutadiene-Incorporated Asymmetric Triphenylamine-Quinoxaline Push-Pull Conjugates.

The excited-state properties of an asymmetric triphenylamine-quinoxaline push-pull system wherein triphenylamine and quinoxaline take up the roles of an electron donor and acceptor, respectively, are initially investigated. Further, in order to improve the push-pull effect, powerful electron acceptors, viz., 1,1,4,4-tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded tetracyanobutadiene (also known as expanded-TCBD or exTCBD), have been introduced into the triphenylamine-quinoxaline molecular framework using a catalyst-free [2 + 2] cycloaddition-retroelectrocyclization reaction. The presence of these electron acceptors caused strong ground-state polarization extending the absorption well into the near-IR region accompanied by strong fluorescence quenching due to intramolecular charge transfer (CT). Systematic studies were performed using a suite of spectral, electrochemical, computational, and pump-probe spectroscopic techniques to unravel the intramolecular CT mechanism and to probe the role of TCBD and exTCBD in promoting excited-state CT and separation events. Faster CT in exTCBD-derived compared to that in TCBD-derived push-pull systems has been witnessed in polar benzonitrile.

Intramolecular Photoinduced Energy and Electron Transfer Reactions in Phenanthroimidazole-Boron Dipyromethane Donor-Acceptor Dyads.

Donor-acceptor systems in which a donor phenanthroimidazole (PhI) is directly connected to a BODIPY acceptor (Dyad1) and separated by an ethynyl bridge between PhI and BODIPY (Dyad2) have been designed, synthesized, and characterized by various spectroscopic and electrochemical techniques. Optical absorption and 1H NMR characteristics of both dyads with those of constituent individuals suggest that there exists a minimum π-π interaction between phenanthroimidazole and BODIPY. Quenched emission of both the dyads was observed when excited either at phenthaoimidazole absorption maxima or at BODIPY absorption maxima in all three investigated solvents. The detailed spectral analysis provided evidence for an intramolecular photoinduced excitation energy transfer (PEnT) from the singlet excited state of phenanthroimidazole to BODIPY and photoinduced electron transfer (PET) from the ground state of phenanthroimidazole to BODIPY. Transient absorption studies suggest that charge-separated species (PhI•+ - BODIPY•-) are generated at a rate constant of (1.16 ± 0.01) × 108 s-1 for the dyads Dyad1 and (5.15 ± 0.03) × 108 s-1 and for Dyad2 whereas energy transfer rate constants were much higher and were on the order of (1.1 ± 0.02) × 1010 s-1 and (1.6 ± 0.02) × 1010 s-1 for Dyad1 and Dyad2, respectively, signifying their usefulness in light energy harvesting applications.