Role of Trap Optimization in a Heterostructure Carbon Nitride as a Methodology to Enhance Photocatalytic Hydrogen Production.

Carbon-based catalysts hold significant promise for photocatalytic hydrogen evolution. A critical challenge lies in optimizing the balance between electron longevity and its accumulation to avoid bottlenecks in photocatalytic efficiency. In this study, we introduce an innovative and efficient strategy for the rapid extraction (<100 fs) of photoinduced free electrons from a carbon-based catalyst without forming additional metal-based heterojunction hybrids.

Excitation-dependent electron exchange energy and electron transfer dynamics in a series of covalently tethered N,N-bis(4'-tert-butylbiphenyl-4-yl)aniline - [C] fullerene dyads via varying π-conjugated spacers.

Femtosecond time-resolved fluorescence and transient absorption studies are reported for three newly synthesized covalently linked N,N-bis(4'-tert-butylbiphenyl-4-yl)aniline (BBA) and pyrrolidinofullerenes (C60)-based donor-π conjugated bridge-acceptor dyads (D-B-A) as functions of the bridge length (7.1, 9.5 and 11.

Direct observation of the rise of delayed fluorescence in dithienylbenzothiadiazole and its role in the excited state dynamics of a donor-acceptor-donor molecule.

Dithienylbenzothiadiazole (DTBT) is used as a building block in several molecules having application in organic light emitting devices (OLED) and organic photovoltaic (OPV) devices. Delayed fluorescence (DF) is the preferred design principle employed currently in OLED research. DTBT has excellent delayed fluorescence properties which makes this moiety a potentially viable OLED material.

Photoinduced bimolecular electron transfer from aromatic amines to pentafluorophenyl porphyrin combined with ultrafast charge recombination persistence with Marcus inverted region.

The dynamics of photoinduced bimolecular reductive electron transfer between meso-tetrakis(pentafluorophenyl)porphyrin (HFTPP), an acceptor (A), and five aromatic amines (donor (D)) with varying oxidation potentials (aniline (AN), N-methylaniline (MAN), N-ethylaniline (EAN), N,N-dimethylaniline (DMAN) and N,N-diethylaniline (DEAN)) in dichloromethane (DCM) as a solvent as well as in neat donor solvents were investigated by employing nanosecond to femtosecond time-resolved fluorescence spectroscopy and femtosecond time-resolved transient absorption spectroscopy upon S excitation of HFTPP. Systematic studies of time-resolved fluorescence quenching dependent on the donor concentration in the concentration range of 0.01-2 M and finally in neat donor solvents broadly enabled us to determine the electron transfer dynamics in three regimes of electron transfer: stationary or diffusion-controlled electron transfer, non-stationary electron transfer and intrinsic or ultrafast electron transfer.

Synthesis and Spectroscopic Investigation of Diketopyrrolopyrrole - Spiropyran Dyad for Fluorescent Switch Application.

We report the synthesis and characterization of a new fluorescent dyad SP-DPP-SP(9) via efficient palladium-catalyzed Sonogashira coupling of prop-2-yn-1-yl 3-(3',3'dimethyl-6-nitrospiro[chromene-2,2'-indolin]-1'-yl)propanoatespiropyran, SP(8), a well known photochromic accepter, with 3,6-bis(5-bromothiophen-2-yl)-2,5-bis((R)-2-ethylhexyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione, DPP(4), a highly fluorescent donor. Under visible light exposure the SP unit is in a closed hydrophobic form, whereas under UV irradiation it converts to a polar, hydrophilic open form named Merocyanine (MC), which is responsible for functioning of photo-switch application. The photochemistry pertaining to fluorescence switch, 'on/off' behaviour, of model dyad SP-DPP-SP(9) is experimentally analyzed in solution as well as in solid state in polymer matrices by photoluminescence(PL) and absorption spectroscopy.

Ultrafast Time-Resolved Emission and Absorption Spectra of meso-Pyridyl Porphyrins upon Soret Band Excitation Studied by Fluorescence Up-Conversion and Transient Absorption Spectroscopy.

A comprehensive study of ultrafast molecular relaxation processes of isomeric meso-(pyridyl) porphyrins (TpyPs) has been carried out by using femtosecond time-resolved emission and absorption spectroscopic techniques upon pumping at 400 nm, Soret band (B band or S2), in 4:1 dichloromethane (DCM) and tetrahydrofuran (THF) solvent mixture. By combined studies of fluorescence up-conversion, time-correlated single photon counting, and transient absorption spectroscopic techniques, a complete model with different microscopic rate constants associated with elementary processes involved in electronic manifolds has been reported. Besides, a distinct coherent nuclear wave packet motion in Qy state is observed at low-frequency mode, ca.

Graphene quantum dots from graphite by liquid exfoliation showing excitation-independent emission, fluorescence upconversion and delayed fluorescence.

Facile synthesis of 2-10 nm-sized graphene quantum dots (GQDs) from graphite powder by organic solvent-assisted liquid exfoliation using a sonochemical method is reported in this study. Synthesized GQDs are well dispersed in organic solvents like ethyl acetoacetate (EAA), dimethyl formamide (DMF) and also in water. MALDI-TOF mass spectrometry reveals its selective mass fragmentation.

A novel FRET 'off-on' fluorescent probe for the selective detection of Fe³⁺, Al³⁺ and Cr³⁺ ions: its ultrafast energy transfer kinetics and application in live cell imaging.

A rhodamine-naphthalimide dyad probe, 1, that selectively responds to the addition of trivalent metal ions (Fe(3+) or Al(3+) or Cr(3+)) via ultrafast Förster resonance energy transfer (FRET) from naphthalimide to rhodamine is designed and synthesized. 1 is highly selective to the trivalent metal ions and the presence of other monovalent or divalent metal ions do not affect its detection ability. The probe is highly sensitive and it can respond to the presence of trivalent metal ions even at sub-micromolar levels.

Ultrafast relaxation dynamics of 5,10,15,20-meso-tetrakis pentafluorophenyl porphyrin studied by fluorescence up-conversion and transient absorption spectroscopy.

The ultrafast photophysical characterization of 5,10,15,20-meso-tetrakis pentafluorophenyl porphyrin (H2F20TPP) in 4:1 dichloromethane (DCM) and tetrahydrofuran (THF) solution has been done in the femtosecond-picosecond time domain, by combining fluorescence up-conversion and femtosecond transient absorption spectroscopy. Fluorescence up-conversion studies on H2F20TPP were done demonstrating fluorescence dynamics over the whole spectral range from 440 to 650 nm when excited at 405 nm, 360.5 cm(-1) excess vibrational energy of Soret band (411 nm).

A naphthalimide based PET probe with Fe3+ selective detection ability: theoretical and experimental study.

A naphthalimide based fluorescent probe '1' that operates based on photoinduced electron transfer phenomenon is synthesized and its chemosensory application is explored. Among various metal ions, 1 selectively detects Fe(3+) with a detection limit of 3.0 × 10(-8) M.

Diffusive and non-diffusive photo-induced proton coupled electron transfer from hydrogen bonded phenols to meso-tetrakis-5,10,15,20-pentafluorophenyl porphyrin.

Enhanced reductive fluorescence quenching of meso-tetrakis-5,10,15,20-pentafluorophenyl porphyrin (H2F20TPP) by two different phenols, 4-methoxy phenol (4-MeOPhOH) and 2,6-dimethoxy phenol (2,6-DiMeOPhOH) in the presence of various pyridine bases in dichloromethane solution is studied using steady state and time resolved fluorescence spectroscopic methods by employing time correlated single photon counting (TCSPC) and fluorescence up-conversion techniques. An enhanced quenching behaviour of H2F20TPP is observed when phenols are hydrogen bonded to various pyridine bases. Quenching observed in the steady state and time resolved studies in the nanosecond time domain follows second order kinetics and generates quenching rate constants and hydrogen bond equilibrium constants, the latter of which agree quite closely with those obtained from independent spectroscopic measurements.

Determination of hydrodynamic properties of bare gold and silver nanoparticles as a fluorescent probe using its surface-plasmon-induced photoluminescence by fluorescence correlation spectroscopy.

Noble-metal nanoparticles labeled with fluorescent molecules are used in a variety of applications requiring the measurement of size and diffusion properties of single nanoprobes. We have successfully used intrinsic surface-plasmon-induced photoluminescence (SPPL) signatures of monodispersed bare gold and silver nanoparticles in water to detect and measure their precise diffusion coefficient, concentration and hydrodynamic radius by fluorescence correlation spectroscopy (FCS). Measurement of the effective hydrodynamic radius confirms particle size to be 80 ± 8 and 64 ± 14 nm for gold and silver, respectively, which is in excellent agreement with scanning electron microscopic measurements made on the same particles.

Role of hydrogen bonding in the photophysical properties of isomeric tetrapyridylporphyrins in aprotic solvent.

Extensive photophysical properties of isomeric tetra-2-pyridylporphyrin (TpyP(2)), tetra-3-pyridylporphyrin (TpyP(3)), and tetra-4-pyridylporphyrin (TpyP(4)) have been studied in the presence of a series of phenols of increasing hydrogen bonding power in dichloromethane solution by employing UV/vis spectroscopy; steady-state, time-resolved fluorescence spectroscopy; and transient absorption spectroscopic techniques. The change of absorption spectra of all three porphyrins as a function of different phenol concentrations established the preference of hydrogen bonded complex formation to the peripheral pyridyl nitrogen rather than the pyrrole nitrogen of the porphyrin macrocycle. The fluorescence behaviors of the porphyrins which were observed upon addition of different phenols point to a marked dependence on the nature of the added phenols.

Reductive fluorescence quenching of the photoexcited free base meso-tetrakis (pentafluorophenyl) porphyrin by amines.

Steady state and time resolved fluorescence quenching behaviors of meso-Tetrakis (pentafluorophenyl) porphyrin (H(2)F(20)TPP) in presence of different aliphatic and aromatic amines have been executed in homogeneous dichloromethane (DCM) solution. At room temperature in DCM, free base (H(2)F(20)TPP) shows fluorescence with two distinct peaks at 640 and 711 nm and natural lifetime tauf=9.8 ns which are very similar to that of meso-tetraphenyl porphyrin (TPP).

Reductive quenching of pyridine linked porphyrins by phenol: a case of proton coupled electron transfer.

PCET is reported for free-base meso-(pyridyl)porphyrins, a pure organic system in dichloromethane solution, by employing UV/Vis and fluorescence spectroscopic techniques.

Density functional studies on the effects of hydrogen bonding on the formation of a charge-transfer complex between p-benzoquinone and 2,6-dimethoxyphenol.

The ability to form a ground-state charge-transfer (CT) complex between an electron acceptor, p-benzoquinone (BQ) and an electron donor, 2,6-dimethoxyphenol (DMOPh) was found to be enhanced by H-bonding of BQ to a hydrogen-bond donor, trifluoroacetic acid (TFA) and H-bonding DMOPh to a hydrogen-bond acceptor, 4-(N,N-dimethylamino)pyridine (DMAPy) [Chem. Phys. Lett.