Dataset Information

Cage^-···Cage^- Interaction: Boron Cluster-Based Noncovalent Bond and Its Applications in Solid-State Materials.

ABSTRACT: Carboranes are boron-carbon clusters with important applications in the fields of materials, catalysis, pharmaceuticals, etc. However, the noncovalent interactions that could determine the solid-state structures and properties of such boron clusters have rarely been investigated. Herein, inspired by the coordinate bond in metallacarborane or ferrocene, the boron cluster-based noncovalent interaction (denoted as cage^-···cage^- interaction) between two nido-carborane clusters was successfully realized by using a pyridinium-based molecular barrier. The X-ray diffraction studies uncover that the cage^-···cage^- interaction has a contacting distance of 5.4-7.0 Å from centroid to centroid in the systems reported here. Theoretical calculations validate the formation of the noncovalent interaction and disclose its repulsive bonding nature that is overcome thanks to the positively charged pyridinium-based framework. Interestingly, such bulk crystalline materials containing the cage^-···cage^- interaction show relevant properties such as full-color absorption in the visible light range and important photothermal effect, which are absent for the control compound without carboranes. This study may offer fundamental insights into the boron cluster-based noncovalent interactions and open a new research avenue to rationally design boron cluster-based materials.

SUBMITTER: Tu D

PROVIDER: S-EPMC8611790 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Similar Datasets

Project description:The Lee-Goldburg condition for homonuclear decoupling in 1H magic-angle spinning (MAS) solid-state NMR sets the angle θ, corresponding to arctan of the ratio of the rf nutation frequency, ν1, to the rf offset, to be the magic angle, θm, equal to tan-1(√2) = 54.7°. At 60 kHz MAS, we report enhanced decoupling compared to MAS alone in a 1H spectrum of 15N-glycine with at θ = 30° for a ν1 of ∼100 kHz at a 1H Larmor frequency, ν0, of 500 MHz and 1 GHz, corresponding to a high chemical shift scaling factor (λCS) of 0.82. At 1 GHz, we also demonstrate enhanced decoupling compared to 60 kHz MAS alone for a lower ν1 of 51 kHz, i.e., a case where the nutation frequency is less than the MAS frequency, with θ = 18°, λCS = 0.92. The ratio of the rotor period to the decoupling cycle time, Ψ = τr/τc, is in the range 0.53 to 0.61. Windowed decoupling using the optimised parameters for a ν1 of ∼100 kHz also gives good performance in a 1H spin-echo experiment, enabling implementation in a 1H-detected 15N-1H cross polarisation (CP)-refocused INEPT heteronuclear correlation NMR experiment. Specifically, initial 15N transverse magnetisation as generated by 1H-15N CP is transferred back to 1H using a refocused INEPT pulse sequence employing windowed 1H decoupling. Such an approach ensures the observation of through-bond N-H connectivities. For 15N-glycine, while the CP-refocused INEPT experiment has a lower sensitivity (∼50%) as compared to a double CP experiment (with a 200 μs 15N to 1H CP contact time), there is selectivity for the directly bonded NH3+ moiety, while intensity is observed for the CH21H resonances in the double CP experiment. Two-dimensional 15N-1H correlation MAS NMR spectra are presented for the dipeptide β-AspAla and the pharmaceutical cimetidine at 60 kHz MAS, both at natural isotopic abundance. For the dipeptide β-AspAla, different build-up dependence on the first spin-echo duration is observed for the NH and NH3+ moieties demonstrating that the experiment could be used to distinguish resonances for different NHx groups.

Dataset Information

Cage^-···Cage^- Interaction: Boron Cluster-Based Noncovalent Bond and Its Applications in Solid-State Materials.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Dataset Information

Cage-···Cage- Interaction: Boron Cluster-Based Noncovalent Bond and Its Applications in Solid-State Materials.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Cage^-···Cage^- Interaction: Boron Cluster-Based Noncovalent Bond and Its Applications in Solid-State Materials.