Photosensitizers for H2 Evolution Based on Charged or Neutral Zn and Sn Porphyrins.

We report a comparison between a series of zinc and tin porphyrins as photosensitizers for photochemical hydrogen evolution using cobaloxime complexes as molecular catalysts. Among all the chromophores tested, only the positively charged zinc porphyrin, [ZnTMePyP4+]Cl4, and the neutral tin porphyrin derivatives, Sn(OH)2TPyP, Sn(Cl2)TPP-[COOMe]4, and Sn(Cl2)TPP-[PO(OEt)2]4, were photocatalytically active. Hydrogen evolution was strongly affected by the pH value as well as the different concentrations of both the sensitizer and the catalyst. A comprehensive photophysical and electrochemical investigation was conducted in order to examine the mechanism of photocatalysis. The results derived from this study establish fundamental criteria with respect to the design and synthesis of porphyrin derivatives for their application as photosensitizers in photoinduced hydrogen evolution.

A meso-meso ß-ß ß-ß Triply Linked Subporphyrin Dimer.

A meso-meso ß-ß ß-ß triply linked subporphyrin dimer 6 was synthesized by stepwise reductive elimination of ß-to-ß doubly PtII -bridged subporphyrin dimer 9. Dimer 6 was characterized by spectroscopic and electrochemical measurements, theoretical calculations, and picosecond time-resolved transient absorption spectroscopy. X-ray diffraction analysis reveals that 6 has a bowl-shaped structure with a positive Gaussian curvature. Despite the curved structure, 6 exhibits a remarkably red-shifted absorption band at 942 nm and a small electrochemical HOMO-LUMO gap (1.35 eV), indicating an effectively conjugated π-electronic network.

First-Generation Subporphyrinatoboron(III) Sensitizers Surpass the 10 % Power Conversion Efficiency Threshold.

Subporphyrinatoboron(III) (SubB) sensitizers were synthesized for use in dye-sensitized solar cells (DSSCs). The prototype, which comprises a sterically demanding 3,5-di-tert-butylphenyl scaffold, a meso-ethynylphenyl spacer, and a cyanoacrylic acid anchoring group, achieved an open-circuit voltage VOC of 836 mV, short-circuit current density JSC of 15.3 mA cm(-2) , fill factor of 0.786, and a photon-to-current conversion efficiency of 10.1 %. Such astonishing figures suggest that a bright future lies ahead for SubB in the realm of DSSCs.

The influence of source molecule structure on the low temperature growth of nitrogen-doped graphene.

Doping of heteroatoms such as nitrogen into the lattice structure of graphene can tune and tailor the overall electronic properties. N-doped graphene, depending on the nitrogen bonding mode and/or bonding configuration, displays subtly altered properties in comparison to pristine graphene. However, there remains a disappointing shortage of reliable methods for introducing dopants in a controlled and reproducible manner, preventing a thorough understanding of the relationship between structure and properties. In this study we aimed to prepare graphenes with nitrogen atoms doped at a graphitic (quaternary) site by depositing a source molecule containing a graphitic nitrogen atom: 4,4,8,8,12,12-hexamethyl-8,12-dihydro-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine or 4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine-4,8,12-trione, on a heated Pt(111) substrate. At 400 °C, graphene with nitrogen atoms exclusively doped at a graphitic site was synthesized from the former molecule, while not from the latter molecule at any temperature. The present result indicates that the rational design of a source molecule is quite important for controlling the nitrogen doped site in the graphene lattice.

Modulating short wavelength fluorescence with long wavelength light.

Two molecules in which the intensity of shorter-wavelength fluorescence from a strong fluorophore is modulated by longer-wavelength irradiation of an attached merocyanine-spirooxazine reverse photochromic moiety have been synthesized and studied. This unusual fluorescence behavior is the result of quenching of fluorophore fluorescence by the thermally stable, open, zwitterionic form of the spirooxazine, whereas the photogenerated closed, spirocyclic form has no effect on the fluorophore excited state. The population ratio of the closed and open forms of the spirooxazine is controlled by the intensity of the longer-wavelength modulated light. Both square wave and sine wave modulation were investigated. Because the merocyanine-spirooxazine is an unusual reverse photochrome with a thermally stable long-wavelength absorbing form and a short-wavelength absorbing photogenerated isomer with a very short lifetime, this phenomenon does not require irradiation of the molecules with potentially damaging ultraviolet light, and rapid modulation of fluorescence is possible. Molecules demonstrating these properties may be useful in fluorescent probes, as their use can discriminate between probe fluorescence and various types of adventitious "autofluorescence" from other molecules in the system being studied.

Probing the rotational dynamics of meso-(2-substituted)aryl substituents in A2B-type subporphyrins.

A2 B-type B-methoxy subporphyrins 3 a-g and B-phenyl subporphyrins 7 a-c,e,g bearing meso-(2-substituted)aryl substituents are synthesized, and their rotational dynamics are examined through variable-temperature (VT) (1) H NMR spectroscopy. In these subporphyrins, the rotation of meso-aryl substituents is hindered by a rationally installed 2-substituent. The rotational barriers determined are considerably smaller than those reported previously for porphyrins. Comparison of the rotation activation parameters reveals a variable contribution of ΔH(≠) and ΔS(≠) in ΔG(≠). 2-Methyl and 2-ethyl groups of the meso-aryl substituents in subporphyrins 3 e, 3 f, and 7 e induce larger rotational barriers than 2-alkoxyl substituents. The rotational barriers of 3 g and 7 g are reduced by the presence of the 4-dibenzylamino group owing to its ability to stabilize the coplanar rotation transition state electronically. The smaller rotational barriers found for B-phenyl subporphyrins than for B-methoxy subporphyrins indicate a negligible contribution of SN 1-type heterolysis in the rotation of meso-aryl substituents.

Intramolecular excimer formation for covalently linked boron dipyrromethene dyes.

Photophysical properties have been recorded for a small series of covalently linked, symmetrical dimers formed around boron dipyrromethene (Bodipy) dyes. Within the series, a control dimer is unable to adopt a cofacial arrangement because of steric factors, while a second dimer possesses sufficient internal flexibility to form the cofacial geometry but with little overlap of the Bodipy units. The other three members of the series take up a cofacial arrangement with varying bite angles between the planes of the two Bodipy units. Fluorescence quantum yields and excited-state lifetimes indicate differing extents of electronic interaction between the two Bodipy head-groups, but only the compound with the smallest bite angle exhibits excimer emission in solution under ambient conditions. Time-resolved fluorescence studies show dual-exponential decay kinetics in each case, while temperature-dependent emission studies reveal reversible coupling between monomer and lower-energy excimer states. The latter is weakly fluorescent, at best, and is seen clearly only for dimers having small bite angles. The application of high pressure to dilute solutions of these dimers promotes excimer formation in certain cases and leads to loss of monomer-like fluorescence. Under high pressure, excimer emission is more evident, and the overall results can be discussed in terms of subtle structural rearrangements that favor excimer formation.

100th Anniversary of Macromolecular Science Viewpoint: Redefining Sustainable Polymers.

Although Staudinger realized makromoleküles had enormous potential, he likely did not anticipate the consequences of their universal adoption. With 6.3 billion metric tons of plastic waste now contaminating our land, water, and air, we are facing an environmental and public health crisis. Synthetic polymer chemists can help create a more sustainable future, but are we on the right path to do so? Herein, a comprehensive literature survey reveals that there has been an increased focus on "sustainable polymers" in recent years, but most papers focus on biomass-derived feedstocks. In contrast, there is less focus on polymer end-of-life fates. Moving forward, we suggest an increased emphasis on chemical recycling, which sees value in plastic waste and promotes a closed-loop plastic economy. To help keep us on the path to sustainability, the synthetic polymer community should routinely seek the systems perspective offered by life cycle assessment.

Exciplex formation and excited state deactivation of difluoroborondipyrromethene (Bodipy) dyads.

Two series of geometrically-related dyads are discussed based on the difluoroborondipyrromethene (Bodipy) unit, and incorporating covalently attached hydroquinone/quinone groups. These units are anchored directly, or via a phenylene spacer, to the Bodipy core at the meso position in one series (BD-MHQ, BD-MQ, BD-MPHQ, BD-MPQ), but for the second series the attachment site is the 2-position (BD-SHQ, BD-SQ, BD-SPHQ, BD-SPQ). The compounds show various levels of fluorescence depending on the oxidation state of the appended group and the substitution pattern. In non-polar solvents such as toluene, diethyl ether and dichlorobenzene, the S(1) state deactivation of the Bodipy unit in BD-SPQ and BD-MPQ is dominated by (1, 3)exciplex formation, which has not been reported for Bodipy derivatives so far. In the latter molecule, the decay of the exciplex is divided between population of the Bodipy triplet state (13 %-21 %) and ground state reformation. This partitioning is not seen for the side-on substituted derivative, BD-SPQ, and only ground state reformation is observed following decay of the exciplex. This difference in behavior is explained by the radical-pair inter-system-crossing mechanism, which more effectively operates in BD-MPQ because of the orthogonality of the donor-acceptor units. In the more polar solvent CH(3)CN all the quinone derivatives show fast formation of the charge-separated state (k(CS)) followed by slower charge recombination (k(CR)). The ratio k(CS)/k(CR)

Cofacial boron dipyrromethene (Bodipy) dimers: synthesis, charge delocalization, and exciton coupling.

A series of compounds containing two boron dipyrromethene (Bodipy) units has been synthesized and fully characterized in which the spacer between the two Bodipy groups is varied from dibenzothiophene (BD1), to dibenzofuran (BD2), to 9,9-dimethylxanthene (BD3), and finally to diphenyl ether (BD4 and BD5). For BD1-BD4 the Bodipy units adopt, to varying degrees, cofacial conformations that allow for systematic variations of both the mutual orientation and the mean separation of the two Bodipy residues. In the remaining dimer, BD5, the Bodipy units are well-separated and cannot come into close proximity. Single-crystal X-ray structures have been determined for BD1-BD3 and reveal that the "bite angle" between the two Bodipy residues decreases progressively along the series with individual values of 41.33(5) degrees, 36.95(6) degrees, and 8.57(3) degrees. Detailed (1)H and (19)F NMR studies for BD3 and BD4 show the methylene protons to be diastereotopic due to restricted rotation of the two Bodipy groups. For BD4 conformational rocking is invoked to explain the variable-temperature NMR spectra, whereby the methyl and methylene groups become inequivalent. Cyclic voltammetry indicates reversible oxidation and reduction of the Bodipy groups. However, the close proximity of the Bodipy groups in BD3 and BD4 results in two well-resolved waves in the anodic region, and slight splitting of the cathodic wave. Peak splitting is attributed to charge delocalization. Spectroelectrochemical measurements at a fixed oxidative potential reveal an optical intervalence charge-transfer (IVCT) absorption band. This IVCT band is attributed to electron exchange between the cofacially arranged neutral and mono-oxidized Bodipy units. Various levels of exciton coupling are observed for BD1-BD4, but not BD5 since here the Bodipy groups remain isolated.

Fast Delayed Emission in New Pyridazine-Based Compounds.

Three novel donor-acceptor molecules comprising the underexplored pyridazine (Pydz) acceptor moiety have been synthesized and their structural, electrochemical and photophysical properties thoroughly characterized. Combining Pydz with two phenoxazine donor units linked via a phenyl bridge in a meta configuration (dPXZMePydz) leads to high reverse intersystem crossing rate k RISC = 3.9 · 106 s-1 and fast thermally activated delayed fluorescence (TADF) with <500 ns delayed emission lifetime. Efficient triplet harvesting via the TADF mechanism is demonstrated in OLEDs using dPXZMePydz as the emitter but does not occur for compounds bearing weaker donor units.

Age at diagnosis, but not HPV type, is strongly associated with clinical course in recurrent respiratory papillomatosis.

BACKGROUND: Recurrent Respiratory Papillomatosis (RRP) is a rare disease characterized by the growth of papillomas in the airway and especially the larynx. The clinical course is highly variable among individuals and there is poor understanding of the factors that drive an aggressive vs an indolent course. METHODS: A convenience cohort of 339 affected subjects with papillomas positive for only HPV6 or HPV11 and clinical course data available for 1 year or more, from a large multicenter international study were included. Exploratory data analysis was conducted followed by inferential analyses with frequentist and Bayesian statistics. RESULTS: We examined 339 subjects: 82% were diagnosed prior to the age of 18 years, 65% were infected with HPV6, and 69% had an aggressive clinical course. When comparing age at diagnosis with clinical course, the probability of aggressiveness is high for children under five years of age then drops rapidly. For patients diagnosed after the age of 10 years, an indolent course is more common. After accounting for confounding between HPV11 and young age, HPV type was minimally associated with aggressiveness. Fast and Frugal Trees (FFTs) were utilized to determine which algorithms yield the highest accuracy to classify patients as having an indolent or aggressive clinical course and consistently created a branch for diagnostic age at ~5 years old. There was no reliable strong association between clinical course and socioeconomic or parental factors. CONCLUSION: In the largest cohort of its type, we have identified a critical age at diagnosis which demarcates a more aggressive from less aggressive clinical course.

A donor-acceptor molecular dyad showing multiple electronic energy-transfer processes in crystalline and amorphous states.

Singlet-singlet, singlet-triplet, and triplet-triplet energy transfer takes place within single crystals and amorphous solid-state solutions of a molecular dyad comprising boron dipyrromethene and oligo-thiophene subunits. The crystal and sublimed thin-films are strongly fluorescent.

Deep-Blue Oxadiazole-Containing Thermally Activated Delayed Fluorescence Emitters for Organic Light-Emitting Diodes.

A series of four novel deep-blue to sky-blue thermally activated delayed fluorescence (TADF) emitters (2CzdOXDMe, 2CzdOXD4MeOPh, 2CzdOXDPh, and 2CzdOXD4CF3Ph) have been synthesized and characterized. These oxadiazole-based emitters demonstrated bluer emission compared with the reference emitter 2CzPN thanks to the weaker acceptor strength of the oxadiazole moieties. The oxadiazole compounds doped in hosts (mCP and PPT) emitted from 435 to 474 nm with photoluminescence quantum yields ranging from 14-55%. The emitters possess singlet-triplet excited-state energy gaps (Δ EST) between 0.25 and 0.46 eV resulting in delayed components ranging from 4.8 to 25.8 ms. The OLED device with 2CzdOXD4CF3Ph shows a maximum external quantum efficiency of 11.2% with a sky-blue emission at CIE of (0.17, 0.25), while the device with 2CzdOXD4MeOPh shows a maximum external quantum efficiency of 6.6% with a deep-blue emission at CIE of (0.15, 0.11).

Intramolecular electron transfer reactions in meso-(4-nitrophenyl)-substituted subporphyrins.

A2B-type meso-(4-nitrophenyl)-substituted subporphyrins have been synthesized and shown to undergo very fast photoinduced intramolecular charge separation (CS) and charge recombination (CR) between the subporphyrin core and the meso-4-nitrophenyl group in CH2Cl2 as probed by femtosecond time-resolved transient absorption spectroscopy. Red-shifted emissions were detected from charge-separated states as a rare case for porphyrinoids.

Analog applications of photochemical switches.

Molecules that change their structure in response to a stimulus such as light or an added chemical can act as molecular switches. Such switches can be chemically linked to other active moieties to create molecular "devices" for various purposes. There has been much activity of late in the use of molecular switches such as photochromes in the construction of molecular logic gates that carry out binary or digital functions. However, ensembles of such molecules can also act as analog devices. Here, examples of a molecular photonic signal transducer and two mimics of photosynthetic photoregulatory processes are discussed.

Lighting the way ahead with boron dipyrromethene (Bodipy) dyes.

This review covers some recent advances made using boron dipyrromethene (Bodipy) compounds, highlighting aspects such as new sensing applications for reactive oxygen species and solvent rheology. The light-harvesting capabilities of the dye especially in the crystalline state are also discussed emphasising Bodipy derivatives as potential candidates for solid-state solar concentrators.