Excited State Quantum Yields Research Articles

Optimization of Triplet Excited State and Singlet Oxygen Quantum Yields of Picolylamine–Porphyrin Conjugates through Zinc Insertion

We synthesized a new class of picolylamine-porphyrin conjugates 1-3 and have investigated the effect of heavy atom insertion on their intersystem crossing efficiency through spin-orbit perturbations. By incorporating zinc ions in the core as well as periphery positions of the porphyrin ring, we have successfully optimized their triplet excited state quantum yields and their efficiency to generate singlet oxygen. Uniquely, the picolylamine-porphyrin conjugate 3 having five zinc ions exhibited a triplet excited state quantum yield of ca. 0.97 and a sensitized singlet oxygen generation yield of ca. 0.92. In contrast, the free base porphyrin derivative 1 exhibited ca. 0.64 and 0.5 of the triplet excited state and singlet oxygen quantum yields, respectively. Our results demonstrate that the insertion of zinc metal ions in the picolylamine-porphyrin conjugates not only quantitatively enhances the triplet excited state and singlet oxygen yields but also imparts hydrophilicity, thereby their potential use as sensitizers in photodynamic therapy and green photooxygenation reactions.

Platinum(II) Complexes Bearing 2‐(9,9‐Dihexadecyl‐7‐R‐fluoren‐2‐yl)‐1,10‐phenanthroline Ligands: Synthesis, Photophysics and Reverse Saturable Absorption

AbstractSix platinum(II) complexes bearing 2‐(9,9‐dihexadecyl‐7‐R‐fluoren‐2‐yl)‐1,10‐phenanthroline ligands (R = NO2, CN, I, H, benzothiazole, thiophene for ligands 1–6, respectively) were synthesized and their photophysics and reverse saturable absorption (RSA) were systematically investigated. All complexes exhibit intense absorption bands between 350 and 450 nm, which are attributed to 1π,π*/1ILCT (intraligand charge transfer) transitions, and broad 1MLCT (metal to ligand charge transfer) transitions between 475 and 550 nm. All complexes are emissive at room temperature in a variety of solvents and at 77 K in butyronitrile glassy matrix, with the long‐lived, structured emission appearing between 600 and 750 nm. The emitting states are assigned to predominantly the 3π,π* state with an admixture of 3MLCT characters. Upon ns laser excitation at 355 nm, all complexes display broad, moderately strong transient absorption from the visible to the near‐IR region. As a result, RSA is observed from all complexes at 532 nm for ns laser pulses. The strength of the RSA for these complexes follows the trend: Pt‐2 > Pt‐3 > Pt‐4 > Pt‐1 >> Pt‐5 > Pt‐6, which correlates well with the trend of the estimated ΦTσex/σ0 values (where ΦT is the triplet excited state quantum yield, and σex and σ0 are the excited‐state and ground‐state absorption cross‐section, respectively) at 532 nm. It is revealed that substitution at the 7‐position of the fluorenyl component exerts a distinct effect on the photophysics and RSA of the complexes. Aromatic substituents such as benzothiazol‐2‐yl and 2‐thionyl cause pronounced red‐shifts of the absorption bands, the emission bands, and the transient difference absorption bands, but a decrease of the RSA at 532 nm.

Photochemical Properties and Reactions with Biomolecules of 4'-N-Acetyl Derivative of Norfloxacin

Abstract The photochemical properties of 4'-N-acetyl derivative of norfloxacin (ANFX) were investigated in different solutions. Both UV-Vis absorption and the quantum yields of excited states are pH-dependent, and pK a value of ground state for the protonation of 3-carboxylic group was determined to be 6.5 ± 0.2. Pulse radiolysis and laser flash photolysis experiments were carried out to characterize transient species of ANFX and to investigate reactions with tryptophan (TrpH) and 2'-seoxyguanosine-5'-monophosphoric acid disodium salt (dGMP). The ANFX undergoes the photoejection of electron by a mixed mechanism of one-photon and two-photon processes. Under moderate laser energy conditions, two-photon process is predominantly. The ANFX radical dianion (ANFX(–H)·2−) formed in reaction with eaq − is characterized by the absorption around 370 nm, and the rate constant was determined to be 1.2 × 1010 dm3 mol−1 s−1. The 3ANFX(–H)−∗ is able to oxidize TrpH and dGMP with bimolecular rate constants of 5.4 × 108 and 9.5 × 106 dm3 mol−1 s−1, respectively. The ANFX(–H)·2− and the oxidized radicals of TrpH and dGMP were observed directly. Under aerobic conditions, the photo-oxidations involve both type I and type II mechanisms.

The examination of berberine excited state by laser flash photolysis

The property of the excited triplet state of berberine (BBR) was investigated by using time-resolved laser flash photolysis of 355nm in acetonitrile. The transient absorption spectra of the excited triplet BBR were obtained in acetonitrile, which have an absorption maximum at 420nm. And the ratio of excitation to ionization of BBR in acetonitrile solvent was calculated. The self-decay and self-quenching rate constants, and the absorption coefficient of 3BBR* were investigated and the excited state quantum yield was determined. Furthermore utilizing the benzophenone (BEN) as a triplet sensitizer, and the β-carotene (Car) as an excited energy transfer acceptor, the assignment of 3BBR* was further confirmed and the related energy transfer rate constants were also determined.

Synthesis and photophysics of 4′-R-2,2′;6′,2″-terpyridyl (R = Cl, CN, N(CH3)2) platinum(II) phenylacetylide complexes

Platinum terpyridyl (tpy) phenylacetylide complexes with -Cl, -CN, and -NMe(2) substituents on the 4'-position of the tpy ligand were synthesized and characterized. Their photophysical properties were systematically investigated. In addition, theoretical electronic structure calculations using density functional theory (DFT) and time-dependent (TD-DFT) approaches were carried out for complexes and ; the results of these calculations provided additional information on the nature of the electronic structures of the low-lying electronic states of these complexes, including the electron density distribution and the composition of the frontier molecular orbitals. Complexes exhibit moderately intense charge-transfer bands in the visible region, which are assigned to the (1)MLCT/(1)LLCT transitions. In comparison to their corresponding chloride complexes , these charge-transfer bands become broadened and red-shifted. Complexes emit at room temperature in CH(3)CN and CH(2)Cl(2) solutions and at 77 K in butyronitrile glassy solutions. At room temperature, the emission is tentatively attributed to (3)MLCT for and , and to a mixture of (3)MLCT/(3)ILCT/(3)pi,pi* for . Due to the admixture of (3)ILCT/(3)pi,pi* characters in its emitting state, displays a much higher emission quantum yield and longer emission lifetime compared to and . Replacing the chloride co-ligand in by phenylacetylide co-ligand clearly enhances the emission and prolongs the lifetime. exhibit a broad and moderately intense triplet excited-state absorption in the visible to the NIR region, with large excited-state absorption coefficients and moderately high triplet excited state quantum yields. Therefore, complexes , especially , have potential applications in organic light emitting devices (OLED) and as reverse saturable absorbing materials.

Synthesis, photophysical and photochemical properties of substituted zinc phthalocyanines

The synthesis, photophysical and photochemical properties of the 4-({3,4,5-tris-[2-(2-ethoxyethoxy)ethyloxy]benzyl}oxy) and 4-({3,4,5-tris-[2-(2-ethoxyethoxy)ethyloxy]benzyl}thio) zinc(ii) phthalocyanines are reported for the first time. The new compounds have been characterized by elemental analysis, IR, (1)H and (13)C NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for photodegradation, singlet oxygen, fluorescence and triplet excited state quantum yields, and triplet state and fluorescence lifetimes of these compounds in dimethylsulfoxide (DMSO). The fluorescence of the complexes was quenched by benzoquinone (BQ). The effects of the substitution on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (6, 7 and 8) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The substituted Zn(II) phthalocyanines showed high triplet and singlet oxygen quantum yields. High singlet oxygen quantum yields are very important for Type II mechanism. Thus, these complexes show potential as Type II photosensitizers.