Synthesis and Anion Binding Assessment of Novel Adamantane Amidopyrroles

Abstract

Two new adamantane anion receptors with amidopyrrole side arms were prepared and their anion binding ability in DMSO solutions with TBA salts (Cl -, AcOand H2PO4 -) was investigated by UV/Vis spectroscopy. After calculating the corresponding association constants of receptor-anion complexes, it became apparent that only one amidopyrrole side arm was engaged in complexation. These experimental findings were rationalized using computational tools and the binding mode was proposed. In addition to the found 1 : 1 stoichiometry, we showed that the studied receptors bind oxo-anions (H2PO4and AcO -) more strongly than spherical halogenide (Cl -) anions.

Supramolecular Chemistry: Exploring the Use of Electronic Structure, Molecular Dynamics, and Machine Learning Approaches

“…Using suit [3]ane, composed of two parallel hexameric platforms alternating three pyridium and three phenyl units connected by p-xylylene bridges (HexaCage + 6 ), as a host and 2,5,8-trihexylbenzotrithiophene (THBTT), and benzotrithiophene (BTT) as a guest, Parreira et al [40] found that the interactions with THBTT has a stabilization of À 69.9 kcal mol À 1 , bigger than the formation of the host-guest complex with BTT. The main contribution to stabilization stems from the London dispersion term, due to an extended π•••π and CÀ H•••π surface given by the benzotrithiophene aromatic core and hexyl chains, as seen by the noncovalent interaction index (NCI) in Figure 6.…”

“…The ability of janusene, a [3,3]ortho-cyclophane, to stabilize Ag + ion was verified by canonical energy decomposition analysis in conjunction with the ETS-NOCV, alongside topological analysis of electron density (QTAIM). The initial results show the capacity to coordinate multiple silver cations, up to five Ag + simultaneously, where thirty-five converged structures as local minima were identified.…”

“…In fact, it has evolved beyond the chemical realm and now interfaces with physics, biology, pharmacy, and engineering. [3][4][5][6] This branch of chemistry encompasses a range of different types of compounds, including host-guest complexes, supramolecular polymers, hydrogels or self-assembled structures held together by reversible noncovalent interactions. [7][8][9] The plethora of intra-and intermolecular noncovalent interactions is responsible for the molecular diversity and complexity in the supramolecular domain.…”

“…Supramolecular chemistry has advanced from aesthetically appealing molecules to innovative chemistry with powerful applications in medicine, catalysis, electronics, and materials science. In fact, it has evolved beyond the chemical realm and now interfaces with physics, biology, pharmacy, and engineering [3–6] . This branch of chemistry encompasses a range of different types of compounds, including host‐guest complexes, supramolecular polymers, hydrogels or self‐assembled structures held together by reversible noncovalent interactions [7–9] .…”

Overcoming barriers with non-covalent interactions: supramolecular recognition of adamantyl cucurbit[n]uril assemblies for medical applications

“…Namely, the adamantane cage is long known to be an efficient scaffold in supramolecular recognition processes, both in chemical and biological systems. 26 Going from our own experience, adamantane and similar cage compounds have demonstrated an amazing versatility and can serve as a backbone in various cation [27][28][29][30][31][32][33][34] and anion receptors [35][36][37][38][39][40][41][42][43][44] as well as being desirable guest molecules in inclusion complexes. [45][46][47][48][49][50][51] While in macrocyclic receptors the adamantane cage usually serves as a rigid backbone that reduces the conformational mobility of a macrocycle and thus pre-organizes the receptor molecule for binding, in the inclusion complexes the role of adamantane is primarily limited to enabling preferential binding of the polycyclic subunit into a host molecules.…”