Co-crystal engineering is a promising method to create new classes of advanced materials. Co-crystal structure prediction is more challenging when one or more of the lattice constituents (tectons) are flexible molecules. This study reports four co-crystals that were prepared by mixing HAuCl 4 or HAuBr 4 with C 3 -symmetric tectons based on a 1,3,5-(methylacetamide)benzene scaffold. X-ray analysis of the co-crystals revealed the presence of three dominant supramolecular interactions; (a) hydrogen bonding between tecton amide NH residues and the AuX 4 − anion, (b) electrostatic stacking of the Au center against the tecton's π-electrons, (c) very short hydrogen bonds within a proton-bridged-carbonyls motif. Within all four co-crystals, the sterically-geared tecton was trapped in a high energy molecular conformation, which increased the number of favorable intermolecular interactions in the lattice. We infer from the results that the likelihood of high energy molecular conformations within a co-crystal increases if there are multiple dominant intermolecular interactions. Application of this generalizable rule should lead to improved crystal structure prediction.
more »
« less
Recognition and applications of anion–anion dimers based on anti-electrostatic hydrogen bonds (AEHBs)
Based on Coulomb's Law alone, electrostatic repulsion between two anions is expected to prevent their dimerization. Contrary to that idea, this Tutorial Review will present evidence showing that anion–anion dimers of protic hydroxyanions can form readily, and describe conditions that facilitate their formation. From X-ray crystal structures, we learn that hydroxyanions dimerize and oligomerize by overcoming long-range electrostatic opposition. Common examples are hydroxyanions of phosphate, sulfate, and carbonate, often in partnership with charged and neutral receptors. Short-range hydrogen bonds between anionic donors and acceptors are defined as anti-electrostatic hydrogen bonds (AEHBs) with insight from theoretical studies. While anion dimers are difficult to identify unequivocally in solution, these solution dimers have recently been definitively identified. The development of the supramolecular chemistry of anion–anion dimers has led to applications in hierarchical assemblies, such as supramolecular polymers and hydrogen bonded organic frameworks.
more »
« less
- Award ID(s):
- 1709909
- NSF-PAR ID:
- 10189156
- Date Published:
- Journal Name:
- Chemical Society Reviews
- ISSN:
- 0306-0012
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract Cryptands utilize inside CH or NH groups as hydrogen bond (H‐bond) donors to capture anions such as halides. In this work, the nature and selectivity of confined hydrogen bonds inside cryptands were computationally analyzed with the energy decomposition scheme based on the block‐localized wavefunction method (BLW‐ED), aiming at an elucidation of governing factors in the binding between cryptands and anions. It was revealed that the intrinsic strengths of inward hydrogen bonds are dominated by the electrostatic attraction, while the anion preferences (selectivity) of inner CH and NH hydrogen bonds are governed by the Pauli exchange repulsion and electrostatic interaction, respectively. Typical conformers of cages are classified into two groups, including the
C 3(h)‐symmetrical conformers, in which all halide anions are located near the centroids of cages, and the “semi‐open” conformers, which exhibit shifted bonding sites for different halide anions. Accordingly, the difference in governing factors of selectivity is attributed to either the rigidity of cages or the binding site of anions for these two groups. In details, theC 3conformers of NH cryptands can be enlarged more remarkably than theC 3(h)‐symmetrical conformers of CH cryptands as the size of anion (ionic radius) increases, resulting in the relaxation of the Pauli repulsion and a dramatic reduction in electrostatic attraction, which eventually rules the selectivity of NH cryptands for halide anions. By contrary, the CH cryptands are more rigid and cannot effectively reduce the Pauli repulsion, which subsequently governs the anion preference. UnlikeC 3conformers whose rigidity determines the selectivity, semi‐open conformers exhibit different binding sites for different anions. From F−to I−, the bonding site shifts toward the outside end of the pocket inside the semi‐open NH cryptand, leading to the significant reduction of the electrostatic interaction that dominates the anion preference. Differently, binding sites are much less affected by the size of anion inside the semi‐open CH cryptand, in which the Pauli exchange repulsion remains the key factor for the selectivity of inner hydrogen bonds. -
Synthetic supramolecular receptors have been widely used to study reversible solution binding of anions; however, few systems target highly-reactive species. In particular, the hydrochalcogenide anions hydrosulfide (HS − ) and hydroselenide (HSe − ) have been largely overlooked despite their critical roles in biological systems. Herein we present the first example of reversible HSe − binding in two distinct synthetic supramolecular receptors, using hydrogen bonds from N–H and aromatic C–H moieties. The arylethynyl bisurea scaffold 1tBu achieved a binding affinity of 460 ± 50 M −1 for HSe − in 10% DMSO- d 6 /CD 3 CN, whereas the tripodal-based receptor 2CF3 achieved a binding affinity of 290 ± 50 M −1 in CD 3 CN. Association constants were also measured for HS − , Cl − , and Br − , and both receptors favored binding of smaller, more basic anions. These studies contribute to a better understanding of chalcogenide hydrogen bonding and provide insights into further development of probes for the reversible binding, and potential quantification, of HSe − and HS − .more » « less
-
more » « less
Rationale Coordinatively driven self‐assembly of transition metal ions and bidentate ligands gives rise to organometallic complexes that usually contain superimposed isobars, isomers, and conformers. In this study, the double dispersion ability of ion mobility mass spectrometry (IM‐MS) was used to provide a comprehensive structural characterization of the self‐assembled supramolecular complexes by their mass and charge, revealed by the MS event, and their shape and collision cross‐section (Ω), revealed by the IM event.
Methods Self‐assembled complexes were synthesized by reacting a bis(terpyridine) ligand exhibiting a 60odihedral angle between the two ligating terpyridine sites (
T ) with divalent Zn, Ni, Cd, or Fe. The products were isolated as (Metal2+[T ])n (PF6)2n salts and analyzed using IM‐MS after electrospray ionization (ESI) which produced several charge states from eachn ‐mer, depending on the number of PF6ˉ anions lost upon ESI. Experimental Ω data, derived using IM‐MS, and computational Ω predictions were used to elucidate the size and architecture of the complexes.Results Only macrocyclic dimers, trimers, and tetramers were observed with Cd2+, whereas Zn2+formed the same plus hexameric complexes. These two metals led to the simplest product distributions and no linear isomers. In sharp contrast, Ni2+and Fe2+formed all possible ring sizes from dimer to hexamer as well as various linear isomers. The experimental and theoretical Ω data indicated rather planar macrocyclic geometries for the dimers and trimers, twisted 3D architectures for the larger rings, and substantially larger sizes with spiral conformation for the linear congeners. Adding PF6ˉ to the same complex was found to mainly cause size contraction due to new stabilizing anion–cation interactions.
Conclusions Complete structural identification could be accomplished using ESI‐IM‐MS. Our results affirm that self‐assembly with Cd2+and Zn2+proceeds through reversible equilibria that generate the thermodynamically most stable structures, encompassing exclusively macrocyclic architectures that readily accommodate the 60oligand used. In contrast, complexation with Ni2+and Fe2+, which form stronger coordinative bonds, proceeds through kinetic control, leading to more complex mixtures and kinetically trapped less stable architectures, such as macrocyclic pentamers and linear isomers.
-
null (Ed.)The ability of a TrCl 4 − anion (Tr = Al, Ga, In, Tl) to engage in a triel bond with both a neutral NH 3 and CN − anion is assessed by ab initio quantum calculations in both the gas phase and in aqueous medium. Despite the absence of a positive σ or π-hole on the Lewis acid, strong triel bonds can be formed with either base. The complexation involves an internal restructuring of the tetrahedral TrCl 4 − monomer into a trigonal bipyramid shape, where the base can occupy either an axial or equatorial position. Although this rearrangement requires a substantial investment of energy, it aids the complexation by imparting a much more positive MEP to the site that is to be occupied by the base. Complexation with the neutral base is exothermic in the gas phase and even more so in water where interaction energies can exceed 30 kcal mol −1 . Despite the long-range coulombic repulsion between any pair of anions, CN − can also engage in a strong triel bond with TrCl 4 − . In the gas phase, complexation is endothermic, but dissociation of the metastable dimer is obstructed by an energy barrier. The situation is entirely different in solution, with large negative interaction energies of as much as −50 kcal mol −1 . The complexation remains an exothermic process even after the large monomer deformation energy is factored in.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0CS00486C
