Ligand Isomerism in Coordination Cages.

Inorg Chem

Department of Chemistry , Indian Institute of Technology Madras, Chennai 600036 , India.

Published: October 2018

Complexation reactions of palladium(II) nitrate with a set of 3-pyridyl appended nonchelating bidentate ligands possessing regioisomeric phenylene-diurea functionalities as spacers were carried out. The ligands utilized in this study are 1,1'-(1,2-phenylene)bis(3-(pyridin-3-yl)urea), L1; 1,1'-(1,3-phenylene)bis(3-(pyridin-3-yl)urea), L2; and 1,1'-(1,4-phenylene)bis(3-(pyridin-3-yl)urea), L3. The complexation reactions of the ligands (L1, L2, and L3) with palladium(II) produced single discrete isomeric cages (1, 2, and 3) of PdL formulation in each case and thereby illustrated ligand-isomerism in coordination cages. All 16 hydrogen atoms of eight urea moieties present in four ligand strands are delineated completely endohedrally in cage 1 and completely exohedrally in cage 3, whereas cage 2 exhibited half of the urea hydrogens in exohedral locations and the remaining half in endohedral locations. In addition to the variable number of solvent molecules, the cavities of cages 1 and 2 lodged four and two nitrate ions, respectively, using the endohedral (H) atoms (i.e., NH groups) as binding sites, whereas the cavity of 3 remained anion free. The abilities of the complexes 1-3 for adsorption of CO gas are demonstrated, and their behaviors are compared.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.inorgchem.8b01884DOI Listing

Publication Analysis

Top Keywords

coordination cages
8
complexation reactions
8
ligand isomerism
4
isomerism coordination
4
cages
4
cages complexation
4
reactions palladiumii
4
palladiumii nitrate
4
nitrate set
4
set 3-pyridyl
4

Similar Publications

This manuscript explores the post-synthetic modification (PSM) of amine-functionalized porous coordination cages, specifically focusing on the formation of imine bonds through reactions with aldehydes. Targeting various cage topologies, including zirconium-, magnesium-, and molybdenum-based structures, we demonstrate the tunability of cage solubility and porosity through selective functionalization where the proximity of amine groups on the parent cage impacts the extent of modification. The work highlights the reversible nature of imine formation, offering potential applications in solubility switching and mixed-metal solid synthesis.

View Article and Find Full Text PDF

In-situ Growth of Metallocluster inside Heterometal-organic Cage to Switch Electron Transfer for Targeted CO2 Photoreduction.

Angew Chem Int Ed Engl

December 2024

Northeast Normal University, Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Institute of Functional Material Chemistry, Local United Engineering Lab for Power Battery, CHINA.

Construction of metal-organic cages (MOCs) with internal modifications is a promising avenue to build enzyme-like cavities and unlocking the mystery of highly catalytic activity and selectivity of enzymes. However, current interests are mainly focused on single-metal-node cages, little achievement has been expended to metalloclusters-based architectures, and the in situ endogenous generation of metal clusters. Herein, based on the hard-soft-acids-bases (HSAB), the metalloclusters-based heterometallic MOC (Cu3VMOP) constructed of [Cu3OPz3]+ and [V6O6(OCH3)9(SO4)(CO2)3]2- clusters was obtained by one-pot method.

View Article and Find Full Text PDF

Charge Manipulation of Porous Coordination Cages Tunes the Efficiency and Selectivity in Electrochemical Synthesis.

Angew Chem Int Ed Engl

December 2024

State Key Laboratory of Chemo/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, 410082, Changsha, Hunan, China.

Electrocatalytic synthesis of high-value chemicals has been attracting growing interest owing to its environmentally benign reaction pathways. Among these processes, the electrocatalytic reduction of nitrate (NO ) to ammonia (NH), known as NORR, and the oxidation of 5-hydroxymethylfurfural (HMFOR) stand out as two cornerstone reactions; yet, their efficiency and selectivity pose ongoing challenges. In this study, we introduce a charge manipulation approach for the design of highly efficient electrocatalysts tailored for the simultaneous coupling of NORR and HMFOR.

View Article and Find Full Text PDF

The rational design and production of a novel series of engineered protein cages are presented, which have emerged as versatile and adaptable platforms with significant applications in biomedicine. These protein cages are assembled from multiple protein subunits, and precise control over their interactions is crucial for regulating assembly and disassembly, such as the on-demand release of encapsulated therapeutic agents. This approach employs a homo-undecameric, ring-shaped protein scaffold with strategically positioned metal binding sites.

View Article and Find Full Text PDF

Cage-catenanes are chemical constructs where two or more cage-like molecules or assemblies are mechanically interlocked together. We report a new class of cage-catenanes where dimeric metal-organic cage-catenanes are linked into larger assemblies through additional bridging metal chloride links. These crystalline materials are obtained from the reaction of tris(nicotinoyl)cyclotriguaiacylene (L1) with Cu(II) salts, and all feature a tetramer of cages where two {Cu(L1)(X)} cages (X=anion) are mechanically interlocked, and link to each other and to another {Cu(L1)(X)} cage-catenane through a planar, linear tetranuclear {Cu(μ-Cl)Cl} cluster.

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!