Control of absorption properties of tetraazaporphyrin group 15 complexes by modification of their axial ligands.

Chem Commun (Camb)

Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.

Published: December 2014

Tetraazaporphyrin (TAP) complexes with group 15 elements (phosphorus(v) or arsenic(v)) containing two axial OH ligands showed reversible spectroscopic changes with acid or base doping. Spectroscopic and theoretical analysis revealed that the modification of axial ligands can tune the interaction between peripheral substituents and the TAP macrocycle.

Download full-text PDF

Source
http://dx.doi.org/10.1039/c4cc07408dDOI Listing

Publication Analysis

Top Keywords

axial ligands
12
modification axial
8
control absorption
4
absorption properties
4
properties tetraazaporphyrin
4
tetraazaporphyrin group
4
group complexes
4
complexes modification
4
ligands tetraazaporphyrin
4
tetraazaporphyrin tap
4

Similar Publications

Unprecedented (2E,4E,6Z,8Z)-nona-2,4,6,8-tetraenoate derivatives highly substituted by aryl groups have been synthesized by the reaction of rhodium complexes having aryl-substituted hexa-1,3,5-trienyl ligands with acrylates. These compounds have potential axial chirality, and their enantiomers are isolable by the chiral HPLC technique. Although the racemization barrier of isolated enantiomers was not high, it was found that a cyclic dimer synthesized by head-to-tail transesterification of a modified analog has quite a stable axial chirality even at a high temperature.

View Article and Find Full Text PDF

Carbonyl complexes of metals with an α-diimine ligand exhibit both emission and ligand-selective photodissociation from MLCT states. Studying this photodissociative mechanism is challenging for experimental approaches due to an ultrafast femtosecond timescale and spectral overlap of multiple photoproducts. The photochemistry of a prototypical system is investigated with non-adiabatic dynamic simulations.

View Article and Find Full Text PDF

Asymmetric Heck Silylation of Unactivated Alkenes.

Angew Chem Int Ed Engl

January 2025

Zhejiang Uiversity, Chemistry, 866 Yuhangtang Road, 310058, Hangzhou, CHINA.

Heck silylation of unactivated alkenes is an efficient strategy for the synthesis of useful organosilicon compounds. However, extensive efforts have been dedicated to only achieving achiral molecules. Herein, a highly regio- and enantioselective cobalt-catalyzed Heck silylation of unactivated alkenes with hydrosilanes is reported for the first time, providing access to axially chiral alkenes in good to excellent yields with 87-98% ee.

View Article and Find Full Text PDF

Electron transfer in polysaccharide monooxygenase catalysis.

Proc Natl Acad Sci U S A

January 2025

California Institute for Quantitative Biosciences, University of California, Berkeley, CA 94720.

Polysaccharide monooxygenase (PMO) catalysis involves the chemically difficult hydroxylation of unactivated C-H bonds in carbohydrates. The reaction requires reducing equivalents and will utilize either oxygen or hydrogen peroxide as a cosubstrate. Two key mechanistic questions are addressed here: 1) How does the enzyme regulate the timely and tightly controlled electron delivery to the mononuclear copper active site, especially when bound substrate occludes the active site? and 2) How does this electron delivery differ when utilizing oxygen or hydrogen peroxide as a cosubstrate? Using a computational approach, potential paths of electron transfer (ET) to the active site copper ion were identified in a representative AA9 family PMO from (PMO9E).

View Article and Find Full Text PDF

Two porphyrin-based polymeric frameworks, SnP-BTC and SnP-BTB, as visible light photocatalysts for wastewater remediation were prepared by the solvothermal reaction of -dihydroxo-[5,15,10,20-tetrakis(phenyl)porphyrinato]tin(IV) (SnP) with 1,3,5-benzenetricarboxylic acid (HBTC) and 1,3,5-tris(4-carboxyphenyl)benzene (HBTB), respectively. The strong bond between the carboxylic acid group of HBTC and HBTB with the axial hydroxyl moiety of SnP leads to the formation of highly stable polymeric architectures. Incorporating the carboxylic acid group onto the surface of SnP changes the conformational frameworks as well as produces rigid structural transformation that includes permanent porosity, good thermodynamic stability, interesting morphology, and excellent photocatalytic degradation activity against AM dye and TC antibiotic under visible light irradiation.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!