Controllable Self-Assembly of V═O Metalloradical Complex with Intramolecular Charge Transfer for Enhanced NIR-II Fluorescence Imaging-Guided Photothermal Therapy.

Near-infrared second region (NIR-II) fluorescence imaging provides enhanced tissue penetration, achieving efficient NIR-II fluorescence and photoacoustic imaging (PA)-guided photothermal therapy (PTT) all in one material remains a challenging yet promising approach in cancer treatment. Herein, open-shell V═O metalloradical complex (VONc) is self-assembled into VONc nanospheres (VONc NPs). VONc NPs exhibit light absorption from 300 to 1400 nm, fluorescence spectra ranging from 900 to 1400 nm, and a distinct fluorescence signal even at 1550 nm.

Hydrogen Atom Abstraction and Reduction Study of 21-Thiaporphyrin and 21,23-Dithiaporphyrin.

The metal-free porphyrins protonation has gained interest over five decades because its structure modification and hardly monoacid intermediate isolation. Here, upon the hydrogen atom abstraction processes, one step diproptonated HSTTP(BF) (STTP = 5,10,15,20-tetraphenyl-21-thiaporphyrin) () and stepwise protonated HSTTPSbCl () and diprotonated HSTTP(BF) () (STTP = 5,10,15,20-tetraphenyl-21,23-thiaporphyrin) compounds were obtained using HSTTP and STTP with oxidants. The closed-shell protonated compounds were fully characterized using XRD, UV-vis, IR and NMR spectra.

Three Oxidation States of Cobalt(I/II/III) Complexes by Thiaporphyrin.

Reaction of tetraphenyl-21-thiaporphyrin (HSTPP) with cobalt salt yields a pentacoordinated high-spin 3/2 [CoCl(STTP)] (). Through ion exchange, a roughly square-planar-geometry low-spin 1/2 CoSTTP(BArF) () complex was isolated. These two paramagnetic precursors were examined by single X-ray diffraction, nuclear magnetic resonance, electron paramagnetic resonance, superconducting quantum interference device, and density functional theory calculations.

Microemulsion-Assisted Self-Assembly of Indium Porphyrin Photosensitizers with Enhanced Photodynamic Therapy.

Designing and constructing supramolecular photosensitizer nanosystems with highly efficient photodynamic therapy (PDT) is vital in the nanomedical field. Despite recent advances in forming well-defined superstructures, the relationship between molecular arrangement in nanostructures and photodynamic properties has rarely been involved, which is crucial for developing stable photosensitizers for highly efficient PDT. In this work, through a microemulsion-assisted self-assembly approach, indium porphyrin (InTPP) was used to fabricate a series of morphology-controlled self-assemblies, including nanorods, nanospheres, nanoplates, and nanoparticles.

Self-Assembled Porphyrin Nanoleaves with Unique Crossed Transportation of Photogenerated Carriers to Enhance Photocatalytic Hydrogen Production.

The preparation of self-assembled porphyrins with orderly stacked nanostructures for emulating natural photosynthesis has stimulated extensive efforts to optimize the energy conversion efficiency. However, the elucidation of how orderly stacked structures promote photocatalysis at the molecular level remains a great challenge. Here, unique porphyrin nanoleaves with designed and ordered structure are synthesized and show a hydrogen evolution rate higher than that of commercial powder.

Ligand Protonation Triggers H Release from a Dinickel Dihydride Complex to Give a Doubly "T"-Shaped Dinickel(I) Metallodiradical.

The dinickel(II) dihydride complex (1 ) of a pyrazolate-based compartmental ligand with β-diketiminato (nacnac) chelate arms (L ), providing two pincer-type {N } binding pockets, has been reported to readily eliminate H and to serve as a masked dinickel(I) species. Discrete dinickel(I) complexes (2 , 2 ) of L are now synthesized via a direct reduction route. They feature two adjacent T-shaped metalloradicals that are antiferromagnetically coupled, giving an S=0 ground state.

Competing H versus Intramolecular C-H Activation at a Dinuclear Nickel Complex via Metal-Metal Cooperative Oxidative Addition.

Nickel(I) metalloradicals bear great potential for the reductive activation of challenging substrates but are often too unstable to be isolated. Similar chemistry may be enabled by nickel(II) hydrides that store the reducing equivalents in hydride bonds and reductively eliminate H upon substrate binding. Here we present a pyrazolate-based bis(β-diketiminato) ligand [L] with bulky -terphenyl substituents that can host two Ni-H units in close proximity.

Reductive O Binding at a Dihydride Complex Leading to Redox Interconvertible μ-1,2-Peroxo and μ-1,2-Superoxo Dinickel(II) Intermediates.

Dioxygen activation at nickel complexes is much less studied than for the biologically more relevant iron or copper systems but promises new reactivity patterns because of the distinct coordination chemistry of nickel. Here we report that a pyrazolate-based dinickel(II) dihydride complex [KL(Ni-H)] (1a) smoothly reacts with O via reductive H elimination to give the μ-1,2-peroxo dinickel(II) complex [KLNi(O)] (2a) and, after treatment with dibenzo[18]-crown-6, the separated ion pair [K(DB18C6)][LNi(O)] (2b); these are the first μ-1,2-peroxo dinickel intermediates to be characterized by X-ray diffraction. In 2a, the K is found side-on associated with the peroxo unit, revealing a pronounced weaking of the O-O bond: d(O-O) = 1.

Pairwise H/D Exchange and H Substitution at a Bimetallic Dinickel(II) Complex Featuring Two Terminal Hydrides.

A compartmental ligand scaffold HL with two β-diketiminato binding sites spanned by a pyrazolate bridge gave a series of dinuclear nickel(II) dihydride complexes M[LNi(H)], M = Na (Na·2) and K (K·2), which were isolated after reacting the precursor complex [LNi(μ-Br)] (1) with MHBEt (M = Na and K). Crystallographic characterization showed the two hydride ligands to be directed into the bimetallic pocket, closely interacting with the alkali metal cation. Treatment of K·2 with dibenzo(18-crown-6) led to the separated ion pair [LNi(H)][K(DB18C6)] (2[K(DB18C6)]).

[A Quantitative Analysis of the Reflectance of the Saline Soil under Different Disturbance Extent].

The reflectance of saline soil in the downstream of No.500 reservoir in Fukang, Xinjiang province was investigated. Through filed sampling and spectral test, using the method of spectral transform, correlation analysis and a quantitative analysis were conducted on the salt and water content of the soil under different disturbance degree.

[Response of Human Respiratory Height PM Variation Characteristics to Meteorological Factors During Winter Haze Days in Beijing].

In order to investigate the influence of meteorological factors on the variation characteristics of PM in Beijing. According to the survey of PM mass concentration in height of human respiration, humidity, the direction of the wind, wind speed and temperature. Using the methods of correlation analysis and nonlinear regression analysis, the effects of meteorological factors on the formation and variation of PM mass concentration in light and moderate air pollution days and heavy pollution were discussed respectively.

Trigonal prismatic Cu(I) and Ag(I) pyrazolato nanocage hosts: encapsulation of S8 and hydrocarbon guests.

Two neutral hexanuclear trigonal prismatic cage molecules have been synthesized by coupling two planar triangular M3pz3-panels, M = Cu(I) and Ag(I), in eclipsed geometry. The ~230 Å(3) cage volume can be either vacant or occupied by neutral guests. The crystal structures of the M6-cyclohexane and Ag6-S8 host-guest species have been determined.