Partha Maity

Extensive Reduction in Back Electron Transfer in Twisted Intramolecular Charge‐Transfer (TICT) Coumarin‐Dye‐Sensitized TiO2 Nanoparticles/Film: A Femtosecond Transient Absorption Study

We report the synthesis, characterization, and optical and electrochemical properties of two structurally similar coumarin dyes (C1 and C2). These dyes have been deployed as sensitizers in TiO2 nanoparticles and thin films, and the effect of molecular structure on interfacial electron-transfer dynamics has been studied. Steady-state optical absorption, emission, and time-resolved emission studies on both C1 and C2, varying the polarity of the solvent and the solution pH, suggest that both photoexcited dyes exist in a locally excited (LE) state in solvents of low polarity. In highly polar solvents, however, C1 exists in an intramolecular charge-transfer (ICT) state, whereas C2 exists in both ICT and twisted intramolecular charge-transfer (TICT) states, their populations depending on the degree of polarity of the solvent and the pH of the solution. We have employed femtosecond transient absorption spectroscopy to monitor the charge-transfer dynamics in C1- and C2-sensitized TiO2 nanoparticles and thin films. Electron injection has been confirmed by direct detection of electrons in the conduction band of TiO2 nanoparticles and of radical cations of the dyes in the visible and near-IR regions of the transient absorption spectra. Electron injection in both the C1/TiO2 and C2/TiO2 systems has been found to be pulse-width limited (<100u2005fs); however, back-electron-transfer (BET) dynamics has been found to be slower in the C2/TiO2 system than in the C1/TiO2 system. The involvement of TICT states in C2 is solely responsible for the higher electron injection yield as well as the slower BET process compared to those in the C1/TiO2 system. Further pH-dependent experiments on C1- and C2-sensitized TiO2 thin films have corroborated the participation of the TICT state in the slower BET process in the C2/TiO2 system.

Super Sensitization: Grand Charge (Hole/Electron) Separation in ATC Dye Sensitized CdSe, CdSe/ZnS Type‐I, and CdSe/CdTe Type‐II Core–Shell Quantum Dots

Ultrafast charge-transfer dynamics has been demonstrated in CdSe quantum dots (QD), CdSe/ZnS type-I core-shell, and CdSe/CdTe type-II core-shell nanocrystals after sensitizing the QD materials by aurin tricarboxylic acid (ATC), in which CdSe QD and ATC form a charge-transfer complex. Energy level diagrams suggest that the conduction and valence band of CdSe lies below the LUMO and the HOMO level of ATC, respectively, thus signifying that the photoexcited hole in CdSe can be transferred to ATC and that photoexcited ATC can inject electrons into CdSe QD, which has been confirmed by steady state and time-resolved luminescence studies and also by femtosecond time-resolved absorption measurements. The effect of shell materials (for both type-I and type-II) on charge-transfer processes has been demonstrated. Electron injection in all the systems were measured to be <150u2005fs. However, the hole transfer time varied from 900u2005fs to 6u2005ps depending on the type of materials. The hole-transfer process was found to be most efficient in CdSe QD. On the other hand, it has been found to be facilitated in CdSe/CdTe type-II and retarded in CdSe/ZnS type-I core-shell materials. Interestingly, electron injection from photoexcited ATC to both CdSe/CdTe type-II and CdSe/ZnS type-I core-shell has been found to be more efficient as compared to pure CdSe QD. Our observation suggests the potential of quantum dot core-shell super sensitizers for developing more efficient quantum dot solar cells.

Restriction of molecular twisting on a gold nanoparticle surface.

To understand the photophysical properties of intramolecular charge transfer (ICT) and twisted intramolecular charge transfer (TICT) states on a gold nanoparticle (Auu2009NP) surface, we have designed and synthesized a new coumarin molecule (C3) that exists both as ICT and TICT states in its excited state in a polar environment. On a Auu2009NP surface, an excited C3 molecule only exists as an ICT state owing to restricted molecular rotation of a diethylamino group; as a result, no conversion from the ICT to TICT state was observed. Selection of the preferential state of a molecule with dual emitting states can be helpful for selected biological applications.

Demonstrating the role of anchoring functionality in interfacial electron transfer dynamics in the newly synthesized BODIPY–TiO2 nanostructure composite

New BODIPY derivatives (dyes 1 and 2) with either catechol or resorcinol functionality, respectively, for anchoring to nanostructured (NS) TiO2 surfaces were synthesized. Extended conjugation at one of the two pyrrole rings at the C3 position helped us to achieve the desired control in tuning the optical and redox properties of the BODIPY based dye molecules. Relative emission quantum yields (Φem1 = ∼52 ± 2% and Φem2 = 54 ± 2%) were found to be much higher in a polar aprotic solvent (acetonitrile) and substantially lower for dye 1 in a polar protic solvent. Steady state optical absorption studies revealed the formation of a strong charge transfer complex between dye 1 and NS-TiO2, while this interaction was much weaker for dye 2. Transient absorption studies were carried out for 1/NS-TiO2 and 2/NS-TiO2 systems following excitation with a laser source of 400 nm to understand the charge transfer dynamics. The results of the transient absorption spectral studies helped us to elucidate the role of anchoring functionality in influencing the dynamics of interfacial electron transfer and charge recombination processes on an ultrafast timescale.

Proton-Coupled Electron-Transfer Processes in Ultrafast Time Domain: Evidence for Effects of Hydrogen-Bond Stabilization on Photoinduced Electron Transfer

The proton-coupled electron-transfer (PCET) reaction is investigated for a newly synthesized imidazole-anthraquinone biomimetic model with a photoactive RuII -polypyridyl moiety that is covalently coupled to the imidazole fragment. Intramolecular H-bonding interactions between imidazole and anthraquinone moieties favor the PCET process; this can be correlated to an appreciable positive shift in the one-electron reduction potential of the coordinated anthraquinone moiety functionalized with the imidazole fragment. This can also be attributed to the low luminescence quantum yield of the RuII -polypyridyl complex used. The dynamics of the intramolecular electron-transfer (ET) and PCET processes are studied by using femtosecond transient absorption spectroscopy. The steady-state spectroscopic studies and the results of the time-resolved absorption studies confirm that H-bonded water molecules play a major role in both ET and PCET dynamics as a proton relay in the excited state. The electron-transfer process is followed by a change in the H-bonding equilibrium between AQ and imidazole in acetonitrile solvent, and protonation of AQ.- by water leads to PCET in the presence of water. A slower forward and backward electron-transfer rate is observed in the presence of D2 O compared with that in H2 O. These results provide further experimental support for a detailed understanding of the PCET process.

Metal–Ligand Complex-Induced Ultrafast Charge-Carrier Relaxation and Charge-Transfer Dynamics in CdX (X=S, Se, Te) Quantum Dots Sensitized with Nitrocatechol

The present work describes the effect of interfacial complex formation on charge carrier dynamics in CdX (X=S, Se, Te) quantum dots (QDs) sensitized nitro catechol (NCAT). To compare experiments were also carried out with catechol (CAT) where no such complexation was observed. Time-resolved emission studies suggest faster charge separation in CdS(Se)/NCAT system as compared to CdS(Se)/CAT although change in Gibbs free energy for hole transfer is less in former as compared to later. This suggests that complex formation favours charge separation. Similar studies were also carried out in CdTe/NCAT system where hole transfer process was not viable thermodynamically but due to complex formation charge separation was observed. Femtosecond transient absorption studies have been carried out to monitor charge carrier dynamics in early time scale. Transient studies show faster electron cooling in QDs/NCAT system as compared to pure QDs and has been assigned to the complex formation on QDs surface. Interestingly charge recombination dynamics is much faster in QDs/NCAT system as compared to pure QDs which can be attributed to the stronger coupling between QDs and NCAT. Our results suggest a strong metal-ligand complex formation on QDs surface that controls charge carrier dynamics in QDs/molecular adsorbate system and to the best of our knowledge it has never been reported.

Slow Electron Cooling Dynamics of Highly Luminescent CdSxSe1-x Alloy Quantum Dot

Ultrafast Electron cooling dynamics of highly luminescent oleic acid caped CdSxSe1-x alloy quantum dot (QD) is investigated by femtosecond transient absorption studies and found to be much slower as compared to pure CdSe and CdS QDs.

Concurrent Ultrafast Electron- and Hole-Transfer Dynamics in CsPbBr3 Perovskite and Quantum Dots

Ultrafast charge-transfer (i.e., electron and hole) dynamics has been investigated between the cesium lead bromide (CsPbBr3, CPB) perovskite nanocrystals (NCs) and cadmium selenide (CdSe) quantum dots (QDs) as a new composite material for photocatalytic and photovoltaic applications. The CPB NCs have been synthesized and characterized by high-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) pattern. The redox levels (i.e., conduction band (CB) and valence band (VB)) of the CPB NCs and CdSe QDs suggest the feasibility of photoexcited electron transfer from CPB NCs to CdSe QDs and photoexcited hole transfer from CdSe QDs to CPB NCs, and it has been confirmed by both steady-state and time-resolved spectroscopy. To investigate the electron- and hole-transfer dynamics in ultrafast time scale, we have performed femtosecond up-conversion and femtosecond transient absorption studies. The measured electron-transfer time from CPB NCs to CdSe QDs and hole-transfer time from CdSe QDs to CPB NCs were found to be 550 and 750 fs, respectively. Interestingly, the charge-transfer process found to be restricted in CPB/CdSe@CdS core-shell system where electron transfer from CPB NCs to core shell takes place, but the hole transfer from core shell to CPB NCs found to be restricted due to CdS shell making the process thermodynamically nonviable. Our observation has suggested that after the photoexcitation of CPB NCs/CdSe QDs composite system, a charge-separated state is formed where the electrons are localized in CB of CdSe QDs and holes are localized in VB of CPB NCs. This makes the composite system a better material for efficient light harvesting and photocatalytic material as compared to the individual ones.

Effect of Molecular Coupling on Ultrafast Electron‐Transfer and Charge‐Recombination Dynamics in a Wide‐Gap ZnS Nanoaggregate Sensitized by Triphenyl Methane Dyes

Wide-band-gap ZnS nanocrystals (NCs) were synthesized, and after sensitizing the NCs with series of triphenyl methane (TPM) dyes, ultrafast charge-transfer dynamics was demonstrated. HRTEM images of ZnS NCs show the formation of aggregate crystals with a flower-like structure. Exciton absorption and lumimescence, due to quantum confinement of the ZnS NCs, appear at approximately 310 and 340u2005nm, respectively. Interestingly, all the TPM dyes (pyrogallol red, bromopyrogallol red, and aurin tricarboxylic acid) form charge-transfer complexes with the ZnS NCs, with the appearance of a red-shifted band. Electron injection from the photoexcited TPM dyes into the conduction band of the ZnS NCs is shown to be a thermodynamically viable process, as confirmed by steady-state and time-resolved emission studies. To unravel charge-transfer (both electron injection and charge recombination) dynamics and the effect of molecular coupling, femtosecond transient absorption studies were carried out in TPM-sensitized ZnS NCs. The electron-injection dynamics is pulse-width-limited in all the ZnS/TPM dye systems, however, the back electron transfer differs, depending on the molecular coupling of the sensitizers (TPM dyes). The detailed mechanisms for the above-mentioned processes are discussed.