We report the H2 uptake properties of six covalent organic frameworks (COFs) from first-principles-based grand canonical Monte-Carlo simulations. The predicted H2 adsorption isotherm is in excellent agreement with the only available experimental result (3.3 vs 3.4 wt % at 50 bar and 77 K for COF-5), also reported here, validating the predictions. We predict that COF-105 and COF-108 lead to a re...

Artificial molecular architecture from a large number of subcomponents (>50) via self-assembly remains a formidable challenge for chemists. Reaction of 38 components [14 Ni(2+) and 24 N-methyl-1-(4-imidazolyl)methanimine] under solvothermal conditions reproducibly leads to the formation of a high-symmetry coordination cage. This polyhedral cage can also be obtained in high yield by self-assembl...

[structure: see text] Three strands of natural collagen are linked by covalent bonds prior to their folding into a triple helix. We report on a synthetic collagen in which the strands are pendent on a rigid macrocyclic scaffold of C(3) symmetry. The scaffold confers substantial conformational stability upon the collagen triple helix and makes its folding independent of concentration, both desir...

Using a novel dynamic covalent approach relying on reversible hydrazone formation, a purely organic 3-dimensional prismatic cage was developed in water at elevated temperatures. By lowering the temperature, the hydrazone bond becomes kinetically inert. This self-assembled cage acts as an effective receptor for donor-acceptor pairs, whose interactions are weak in the absence of the cage.

A novel [3]rotaxane composed of two 25-membered crownophanes and one axle molecule having two anthryl end groups was successfully synthesized via covalent bond formation followed by aminolysis, and can incorporate caesium ion into the space between the two macrocycles as a 1 : 1 sandwich-type complex, whereas it makes a 1 : 2 complex with lithium ion.

The study aimed to cast light on the structure and internal energetics of guanine- and xanthine-based model DNA quadruplexes and the physico-chemical nature of the non-covalent interactions involved. Several independent approaches were used for this purpose: DFT-D3 calculations, Quantum Theory of Atoms in Molecules, Natural Bond Orbital Analysis, Energy Decomposition Analysis, Compliance Consta...

Covalent organic frameworks are a class of crystalline porous polymers that integrate molecular building blocks into periodic structures and are usually synthesized using two-component [1+1] condensation systems comprised of one knot and one linker. Here we report a general strategy based on multiple-component [1+2] and [1+3] condensation systems that enable the use of one knot and two or three...

Electrostatic (through-space) and covalent (through-bond) contributions to couplings involving the C[double bond]O and C[bond]N vibrational stretching modes of the amide group in the alpha-helix and the parallel and antiparallel beta-sheet structures of alanine polypeptides are analyzed. Coupling constants computed at the density functional theory level are compared with the transition dipole c...

Long-range non-covalent interactions play a key role in the chemistry of natural polyphenols. We have previously proposed a description of supramolecular polyphenol complexes by the B3P86 density functional coupled with some corrections for dispersion. We couple here the B3P86 functional with the D3 correction for dispersion, assessing systematically the accuracy of the new B3P86-D3 model using...