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A set of Pd(II) biladiene complexes bearing different combinations of methyl- and phenyl-substituents on the sp3-hybridized meso-carbon (the 10-position of the biladiene framework) was prepared and studied. In addition to a previously described Pd(II) biladiene complex bearing geminal dimethyl substituents a the 10-position (Pd[DMBil]), homologous Pd(II) biladienes bearing geminal methyl and phenyl substituents (Pd[MPBil1]) and geminal diphenyl groups(Pd[DPBil1]) were prepared and structurally characterized. Detailed electrochemical as well as steady-state and time-resolved spectroscopic experiments were undertaken to evaluate the influence of the substituents on the biladiene's tetrahedral meso-carbon. Although all three biladiene homologues are isostructural, Pd[MPBil1] and Pd[DPBil1] display more intense absorption profiles that shift slightly toward lower energies as geminal methyl groups are replaced by phenyl rings. All three biladiene homologues support a triplet photochemistry, and replacement of the geminal dimethyl substituents of Pd[DMBil1] (ΦΔ = 54%) with phenyl groups improves the ability of Pd[MPBil1] (ΦΔ = 76%) and Pd[DPBil1] (ΦΔ = 66%) to sensitize 1O2. Analysis of the excited-state dynamics of the Pd(II) biladienes by transient absorption spectroscopy shows that each complex supports a long-lived triplet excited-state (i.e., τ > 15 μs for each homologue) but that the ISC quantum yields (ΦT) varied as a function of biladiene substitution. The observed trend in ISC efficiency matches that for singlet oxygen sensitization quantum yields (ΦΔ) across the biladiene series considered in this work. The results of this study provide new insights to guide future development of biladiene based agents for PDT and other photochemical applications.

The COVID-19 pandemic has had far-reaching impacts on public health and safety, economics, and the transportation system. To reduce the spread of this disease, federal and local governments around the world have introduced stay-at-home orders and other restrictions on travel to “non-essential” businesses to implement social distancing. Preliminary evidence suggests substantial variability in the impacts of these orders in the United States, both across states and over time. This study examines this issue using daily county-level vehicle miles traveled (VMT) data for the 48 continental U.S. states and the District of Columbia. A two-way random effects model is estimated to assess changes in VMT from March 1 to June 30, 2020 as compared with baseline January travel levels. The implementation of stay-at-home orders was associated with a 56.4 percent reduction in VMT on average. However, this effect was shown to dissipate over time, which may be attributable to “quarantine fatigue.” In the absence of full shelter-in-place orders, travel was also reduced where restrictions on select businesses were introduced. For example, restrictions on entertainment, indoor dining, and indoor recreational activities corresponded to reductions in VMT of 3 to 4 percent while restrictions on retail and personal care facilities showed 13 percent lower traffic levels. VMT was also shown to vary based on the number of COVID case reports, as well as with respect to other characteristics, including median household income, political leanings, and how rural the county was in nature.

Photothermal therapy (PTT) is a promising treatment option for diseases, including cancer, arthritis, and periodontitis. Typical photothermal agents (PTAs) absorb light in the near-infrared (NIR)-I region of 650-900 nm with a predominant focus around 800 nm, as these wavelengths are minimally absorbed by water and blood in the tissue. Recently, interest has grown in developing nanomaterials that offer more efficient photothermal conversion and that can be excited by light close to or within the NIR-II window of 1000-1700 nm, which offers less absorption by melanin. Herein, we report on the development of 5,5-diphenyl isocorrole (

The selective 4e

The selective 4e–/4H+ reduction of dioxygen to water is an important reaction that takes place at the cathode of fuel cells. Monomeric aromatic tetrapyrroles (such as porphyrins, phthalocyanines, and corroles) coordinated to Co(II) have been considered as oxygen reduction catalysts due to their low cost and relative ease of synthesis. How- ever, these systems have been repeatedly shown to be selective for O2 reduction by the less desired 2e –/2H+ pathway to yield hydrogen peroxide. Herein, we report the initial synthesis and study of a Co(II) tetrapyrrole complex based upon a non-aromatic isocorrole scaffold that is competent for 4e–/4H+ ORR. This Co(II) 10,10-dimethyl isocorrole (Co[10- DMIC]) is obtained in a just four simple steps and excellent yield from a known dipyrromethane synthon. Evaluation of the steady state spectroscopic and redox properties of Co[10-DMIC] against those of Co(II) porphyrin ([Co(TPFPP)]) and corrole ([Co(TPFPC)(PPh3)]) homologs demonstrated that the light harvesting and electrochemical properties of the isocorrole are distinct from those displayed by more traditional aromatic tetrapyrroles. Further, investigation of the ORR activity of Co[10-DMIC] using a combination of electrochemical and chemical reduction studies revealed that this simple, unadorned monomeric Co(II) tetrapyrrole is ~85% selective for the 4e–/4H+ reduction of O2 to H2O over the more kinetically facile 2e–/2H+ process that delivers H2O2. By contrast, the same ORR evaluations conducted for the Co(II) porphyrin and corrole homologs demonstrated that these traditional aromatic systems catalyze the 2e–/2H+ conversion of O2 to H2O2 with near complete selectivity. Despite being a simple, easily prepared, monomeric tetrapyrrole platform, Co[10-DMIC] supports an ORR catalysis that has historically only been achieved using elaborate porphyrinoid-based architectures that incorporate pendant proton-transfer groups, ditopic molecular clefts, or which impose cofacially ori- ented O2 binding sites. Accordingly, Co[10-DMIC] represents the first simple, unadorned, monomeric metalloisocorrole complex that can be easily prepared and which shows a privileged performance for the 4e–/4H+ peractivation of O2 to water as compared to other simple Co(II) tetrapyrroles.

A set of Pd(II) biladiene complexes bearing different combinations of methyl- and phenyl-substituents on the sp

Via conversion to Katritzky pyridinium salts, alkyl amines can now be used as alkyl radical precursors for a range of deaminative functionalization reactions. The key step of all these methods is single electron reduction of the pyridinium ring, which triggers C-N bond cleavage. However, little has been done to understand how the precise nature of the pyridinium influences these events. Using a combination of synthesis, computation, and electrochemistry, this study delineates the steric and electronic effects that substituents have on the canonical steps and the overall process. Depending on the approach taken, consideration of both the reduction and the subsequent radical dissociation may be necessary. Whereas the electronic effects on these steps work in opposition to each other, the steric effects are synergistic, with larger substituents favoring both steps. This understanding provides a framework for future design of pyridinium salts to match the mode of catalysis or activation.

Two brominated 10,10-dimethylisocorrole (10-DMIC) derivatives containing Pd(II) centers have been prepared and characterized. These compounds were prepared via bromination of 10,10-dimethylbiladiene-based oligotetrapyrroles. Bromination of free base 10,10-dimethylbiladiene (DMBil1) followed by metalation with Pd(OAc)(2), as well as bromination of the corresponding Pd(II) dimethylbiladiene complex (Pd[DMBil1]) provide routes to Pd(II) hexabromo-10,10-dimethyl-5,15-bis(pentafluorophenyl)-isocorrole (Pd[10-DMIC-Br(6)]) and Pd(II) octabromo-10,10-dimethyl-5,15-bis(pentafluorophenyl)-isocorrole (Pd[10-DMIC-Br(8)]). The solid-state structures of the two brominated isocorrole complexes are presented, as is that for a new decabrominated dimethylbiladiene derivative (DMBil-Br(10)). The electronic and spectroscopic properties of the brominated biladiene and isocorrole derivatives were probed using a combination of voltammetric methods and steady-state UV–vis absorption and emission experiments. Data obtained from these experiments allow the properties of the brominated biladiene and isocorrole derivatives to be compared to previously studied biladiene derivatives (i.e., DMBil1 and Pd[DMBil1]). CV and DPV experiments demonstrate that Pd[10-DMIC-Br(6)] and Pd[10-DMIC-Br(8)] support well-behaved multielectron redox chemistry, similar to that which has been observed for other nonaromatic tetrapyrroles containing sp(3)-hybridized meso-carbons. Spectroscopic experiments reveal that bromination of the dimethylbiladiene core shifts this system’s UV–vis absorption profile to lower energy and that the dimethylisocorrole complexes support panchromatic absorption profiles that extend across the UV–vis and into the near-IR region. Photosensitization experiments demonstrate that unlike previously studied Pd(II) biladiene constructs, DMBil-Br(10), Pd[10-DMIC-Br(6)], and Pd[10-DMIC-Br(8)] support limited triplet excited state chemistry with O(2), indicating that the novel nonaromatic tetrapyrrole derivatives described in this work may be best suited for applications other than singlet oxygen sensitization.

An efficient, one-pot and multi-component synthesis of trans -perfluoroalkylated [1,3]oxazino[2,3- a ]isoquinoline derivatives is described. Moderate to excellent yields have been achieved under mild conditions. A plausible mechanism for this type of cyclization is proposed. In addition, isoquinolines as the nucleophilic reagent have been examined. Furthermore, excellent regioselectivity and diastereoselectivity can be observed in this reaction.

A multicomponent reaction involving quinolines, methyl perfluoroalk-2-ynoates and aromatic aldehydes for the synthesis of perfluoroalkylated fused [1,3]oxazine derivatives has been described. The whole process is carried out under mild conditions and furnishes the desired products in good yields. Furthermore, excellent regioselectivity and diastereoselectivity can be observed in this reaction.

An efficient, one-pot, three-component procedure for the synthesis of fluorinated oxazinoisoquinolines with excellent regioselectivity and diastereoselectivity is presented.

A new multicomponent reaction involving methyl perfluoroalk-2-ynoates, quinolines and aldehydes leading to the sole formation of cis-perfluoroalkylated [1,3]oxazino[3,2-α]quinolines, is developed.