Manipulating metal-ligand binding in allosteric coordination complexes through ring strain.

Chem Commun (Camb)

Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, USA.

Published: January 2025


Category Ranking

98%

Total Visits

921

Avg Visit Duration

2 minutes

Citations

20

Article Abstract

The weak-link approach (WLA) to organometallic complexes offers a powerful method to create allosteric shape-shifting coordination complexes. However, chemically tuning the metal-ligand interactions entails challenging syntheses. This study explores the influence of ring strain on the lability of the platinum-sulfur interaction within WLA complexes, providing a simpler alternative to chemical modifications. We study the relationship of ring size, and subsequent reactivity within 4- to 8-membered WLA cyclic Pt coordination complexes through solution and solid-state studies. These results show that strain can direct the energetic preference for the desired allosteric states and therefore, the choice of small molecule effectors required to facilitate such interconversions.

Download full-text PDF

Source
http://dx.doi.org/10.1039/d4cc06135gDOI Listing

Publication Analysis

Top Keywords

coordination complexes
12
ring strain
8
complexes
5
manipulating metal-ligand
4
metal-ligand binding
4
binding allosteric
4
allosteric coordination
4
complexes ring
4
strain weak-link
4
weak-link approach
4

Similar Publications

The gas-phase structures of dibenzo-24-crown-8 (DB24C8) and dinaphtho-24-crown-8 (DN24C8) complexes with divalent metal ions (Mg, Ca, Sr, Ba, Fe, Ni, and Zn) were investigated by cryogenic ion mobility-mass spectrometry (IM-MS) in combination with density functional theory calculations. Several complexes, particularly those of DN24C8, exhibited multiple coexisting conformers. DFT-optimized structures were classified based on the relative orientation of the two aromatic rings in the crown ether.

View Article and Find Full Text PDF

The unit cell of the title compound, [Ni(CHNO)]·2CHOH, consists of a neutral complex and two methanol mol-ecules. In the complex, the two tridentate 2-[3-(benzo[][1,3]dioxol-5-yl)-1-1,2,4-triazol-5-yl]-6-(1-pyrazol-1-yl)pyridine ligands coordinate to the central Ni ion through nitro-gen atoms of the pyrazole, pyridine and triazole groups, forming a pseudo-octa-hedral coordination sphere. Neighbouring mol-ecules are linked through weak C-H(pz)⋯π(ph) inter-actions into monoperiodic chains, which are further linked through weak C-H⋯H/N/C inter-actions into diperiodic layers.

View Article and Find Full Text PDF

-functionalization of tailored-adaptive nanospace for efficient binding of organic molecules in non-aqueous media.

Natl Sci Rev

September 2025

Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710127, China.

Precision in controlling the microenvironment of nanospaces is a potent strategy for exploring architecture‒function relationships. Herein, a face-capped tetrahedral cage, featuring Pd‒Pd-bonded vertices, with a tailored nanospace surrounded by 12 ethyl units, was facilitated to adaptively accommodate a library of guests with different sizes and shapes, including C6 cyclic hydrocarbons, adamantane derivatives, S and P. This nanocavity can achieve strong binding with cyclohexane in non-aqueous media in contrast to reported structurally similar non--functionalized cages by an increase of four orders of magnitude.

View Article and Find Full Text PDF

In this study, we synthesized a series of novel -acetyl Schiff bases (-) containing 1,2,4-triazole moiety and evaluated their potential as anticancer agents through both experimental and computational approaches. Cytotoxicity assays on prostate cancer (PC) (DU145) and normal epithelial cells (PNT1a) demonstrated selective inhibition, particularly for compounds , , and , with IC values of 73.25, 49.

View Article and Find Full Text PDF

Background: Results from the GEMSTONE-303 trial indicate that compared with placebo plus capecitabine and oxaliplatin (PLA-CAP), sugemalimab plus capecitabine and oxaliplatin (SUG-CAP) as first-line therapy provides clinical benefits for patients with advanced gastric or gastroesophageal junction (G/GEJ) adenocarcinoma with programmed cell death ligand 1 (PD-L1) combined positive score (CPS) ≥5. However, the addition of sugemalimab increases medical costs. This study aimed to assess the cost-effectiveness of SUG-CAP vs.

View Article and Find Full Text PDF