Dataset Information

Mechanochemical Preparation of Dipyridyl-Naphthalenediimide Cocrystals: Relative Role of Halogen-Bond and π-π Interactions.

ABSTRACT: Naphthalenediimide derivates are a class of π-conjugated molecules largely investigated in the literature and used as building blocks for metal-organic frameworks or coformers for hydrogen-bond-based cocrystals. However, their tendency to establish halogen-bond interactions remains unexplored. By using a crystalline engineering approach, we report here four new cocrystals with N,N'-di(4-pyrydyl)-naphthalene-1,4,5,8-tetracarboxidiimide and diiodo-substituted coformers, easily obtained via a mechanochemical protocol. Cocrystals were characterized via NMR, electron ionization mass spectrometry, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Crystallographic structures were then finely examined and correlated with energy framework calculations to understand the relative contribution of halogen-bond and π-π interactions toward framework stabilization.

SUBMITTER: Mazzeo PP

PROVIDER: S-EPMC8498987 | biostudies-literature | 2021 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Mechanochemical Preparation of Dipyridyl-Naphthalenediimide Cocrystals: Relative Role of Halogen-Bond and π-π Interactions.

Mazzeo Paolo P PP Pioli Marianna M Montisci Fabio F Bacchi Alessia A Pelagatti Paolo P

Crystal growth & design 20210901 10

Naphthalenediimide derivates are a class of π-conjugated molecules largely investigated in the literature and used as building blocks for metal-organic frameworks or coformers for hydrogen-bond-based cocrystals. However, their tendency to establish halogen-bond interactions remains unexplored. By using a crystalline engineering approach, we report here four new cocrystals with <i>N</i>,<i>N</i>'-di(4-pyrydyl)-naphthalene-1,4,5,8-tetracarboxidiimide and diiodo-substituted coformers, easily obtain ...[more]

PMID: 34650338

Similar Datasets

Project description:Recently, noncovalent interactions in complexes and crystals have attracted considerable interest. The current study was thus designed to gain a better understanding of three seminal types of noncovalent interactions, namely: hydrogen, halogen and tetrel interactions with π-systems. This study was performed on three models of Lewis acids: X3-C-H, F3-C-X and F-T-F3 (where X = F, Cl, Br and I; and T = C, Si, Ge and Sn) and three π-systems as Lewis bases: benzene (BZN), 1,3,5-trifluorobenzene (TFB) and hexafluorobenzene (HFB). Quantum mechanical calculations, including geometrical optimization, molecular electrostatic potential (MEP), maximum positive electrostatic potential (V s,max), Point-of-Charge (PoC), potential energy surface (PES), quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) calculations, were carried out at the MP2/aug cc-pVDZ level of theory. The binding energies were additionally benchmarked at the CCSD(T)/CBS level. The results showed that: (i) the binding energies of the X3-C-H⋯π-system complexes were unexpectedly inversely correlated with the V s,max values on the hydrogen atom but directly correlated with the X atomic sizes; (ii) the binding energies for the F3-C-X⋯π-system and F-T-F3⋯π-system complexes were correlated with the σ-hole magnitudes of the X and T atoms, respectively; and (iii) for the F3-C-F⋯π-system complexes, the binding energy was as strong as the π-system was electron-deficient, indicating the dominating nucleophilic character of the fluorine atom. NCI analysis showed that the unexpected trend of X3-C-H⋯π-system binding energies could be attributed to additional attractive interactions between the X atoms in the X3-C-H molecule and the carbon atoms of the π-system. Furthermore, the I3-Sn-H molecule was employed as a case study of hydrogen, halogen and tetrel interactions with π-systems. It was found that hydrogen and halogen interactions of the I3-Sn-H molecule correlated with the electron-richness of the π-system. In contrast, tetrel interactions correlated with the electron deficiency of the π-system.

Dataset Information

Mechanochemical Preparation of Dipyridyl-Naphthalenediimide Cocrystals: Relative Role of Halogen-Bond and π-π Interactions.

Publications

Mechanochemical Preparation of Dipyridyl-Naphthalenediimide Cocrystals: Relative Role of Halogen-Bond and π-π Interactions.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets