Weak interactions in crystals: old concepts, new developments

Batsanov, Andrei S.

doi:10.1107/s2056989018005339

Cited by 14 publications

(8 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…From these data, a thermal expansion coefficient α V = 2.54 × 10 −4 K −1 can be calculated for crystals of 1, 37 consistent with the expectation for organic crystals. 57 Over the selected temperature range (90−270 K), the emission peak energy increases by 1288 cm −1 (i.e., the emission peak is blue-shifted by 52 nm).…”

Section: ■ Resultsmentioning

confidence: 98%

Toward Opto-Structural Correlation to Investigate Luminescence Thermometry in an Organometallic Eu(II) Complex

et al. 2022

View full text Add to dashboard Cite

Lanthanide-based luminescent materials have unique properties and are well-studied for many potential applications. In particular, the characteristic 5d → 4f emission of divalent lanthanide ions such as EuII allows for tunability of the emissive properties via modulation of the coordination environment. We report the synthesis and photoluminescence investigation of pentamethylcyclopentadienyleuropium(II) tetrahydroborate bis(tetrahydrofuran) dimer (1), the first example of an organometallic, discrete molecular EuII band-shift luminescence thermometer. Complex 1 exhibits an absolute sensitivity of 8.2 cm–1 K–1 at 320 K, the highest thus far observed for a lanthanide-based band-shift thermometer. Opto-structural correlation via variable-temperature single-crystal X-ray diffraction and fluorescence spectroscopy allows rationalization of the remarkable thermometric luminescence of complex 1 and reveals the significant potential of molecular EuII compounds in luminescence thermometry.

show abstract

Section: ■ Resultsmentioning

confidence: 98%

Toward Opto-Structural Correlation to Investigate Luminescence Thermometry in an Organometallic Eu(II) Complex

et al. 2022

View full text Add to dashboard Cite

show abstract

“…He also described these weak interactions as what keeps the organic world together. [49,50] Interactions such as hydrogen bonding; strong (2.2-2.5Å), intermediate (2.5-3.2Å) and weak (3.2-4.0 Å) with angle cutoffs > 90 degree, [51] π−π stacking (either in a flat configuration with face-to-face arrangement or edge configuration with edge-to-face arrangements), [52][53][54] electrostatic, hydrophobic, charge transfer, metal coordination, halogen bonding, and metallophilic interactions [55] interconnect molecules in the lattice via different supramolecular synthons discussed in the previous paragraphs. Molecular recognition (which is a necessary complementarity between molecules forming an aggregate) is compulsory in this formation and stabilization of supramolecular systems.…”

Section: Co-former Selection and Co-crystal Designmentioning

confidence: 99%

Pharmaceutical co‐crystal: An alternative strategy for enhanced physicochemical properties and drug synergy

Ngilirabanga

Samsodien

2021

Nano Select

View full text Add to dashboard Cite

A growing number of co-crystals in the literature are proof of how significant the co-crystallization concept has become. Co-crystallization enhances physicochemical properties through the formation of intermolecular interactions between a drug and a co-former. A co-crystal is a single crystalline material consisting of at least two molecular components solid at room temperature and present in a definite stoichiometric ratio. Pharmaceutical co-crystals consist of the active pharmaceutical ingredient and the co-former selected from generally regarded as safe (GRAS) list of the United State Food and Drug Administration. Co-crystal formation requires an understanding of a drug target, a proper choice of a co-former and is only achieved experimentally after several trials. Other beneficial co-crystallization outcomes include binary eutectics, solid dispersions, amorphous forms, etc. Several key issues including design strategies, co-former selection, and co-crystallization methods; tradition and newly synthetic methods that are more efficient and suitable for large scale have been briefly described. The co-crystal preference is demonstrated with a particular emphasis on multidrug co-crystals and their contribution to the drug combination strategies used for the treatment and management of drug resistance and adverse side effects in serious medical conditions that require the administration of high doses such as HIV/AIDS, tuberculosis, and others. K E Y W O R D S co-crystal development, co-crystallization, design, pharmaceutical co-crystals, preferences, synergistic co-crystals 1 INTRODUCTION Less than 1% of active pharmaceutical ingredients (APIs) reach the market because of poor biopharmaceutical properties among which solubility plays a key role. [1] Poor physicochemical properties of APIs such as chemical stability, dissolution, hygroscopicity, and solubility impact This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

show abstract

“…As such, it emphasizes akey aspect of NCI "ecosystems", that is,t hat strong and weak interactions cooperate to form the observed equilibrium structures. [29] From am ethodological point of view,t his study suggests that QM calculations on model systems may not always be able to accurately determine non-covalent interaction distances if these interactions,within the full structural context, are affected by compression or other structural effects. [30] However,i tu nderlines,t hrough at horough comparison between calculated and experimental data, the usefulness of high-quality QM calculations in determining where such effects may be effective.…”

Section: Forschungsartikelmentioning

confidence: 99%

Short but Weak: The Z‐DNA Lone‐Pair⋅⋅⋅π Conundrum Challenges Standard Carbon Van der Waals Radii

et al. 2020

View full text Add to dashboard Cite

Current interest in lone‐pair⋅⋅⋅π (lp⋅⋅⋅π) interactions is gaining momentum in biochemistry and (supramolecular) chemistry. However, the physicochemical origin of the exceptionally short (ca. 2.8 Å) oxygen‐to‐nucleobase plane distances observed in prototypical Z‐DNA CpG steps remains unclear. High‐level quantum mechanical calculations, including SAPT2+3 interaction energy decompositions, demonstrate that lp⋅⋅⋅π contacts do not result from n→π* orbital overlaps but from weak dispersion and electrostatic interactions combined with stereochemical effects imposed by the locally strained structural context. They also suggest that the carbon van der Waals (vdW) radii, originally derived for sp3 carbons, should not be used for smaller sp2 carbons attached to electron‐withdrawing groups. Using a more adapted carbon vdW radius results in these lp⋅⋅⋅π contacts being no longer of the sub‐vdW type. These findings challenge the whole lp⋅⋅⋅π concept that refers to elusive orbital interactions that fail to explain short interatomic contact distances.

show abstract

Weak interactions in crystals: old concepts, new developments

Abstract: Andrei Batsanov presents a general review of weak interactions in crystals, which highlights the history, state-of-the art and future developments of this field.

Cited by 14 publications

References 47 publications

Toward Opto-Structural Correlation to Investigate Luminescence Thermometry in an Organometallic Eu(II) Complex

Toward Opto-Structural Correlation to Investigate Luminescence Thermometry in an Organometallic Eu(II) Complex

Pharmaceutical co‐crystal: An alternative strategy for enhanced physicochemical properties and drug synergy

Short but Weak: The Z‐DNA Lone‐Pair⋅⋅⋅π Conundrum Challenges Standard Carbon Van der Waals Radii

Contact Info

Product

Resources

About