Dicarboxylate recognition based on ultracycle hosts through cooperative hydrogen bonding and anion–π interactions

• Wen-Hui Mi,
• Teng-Yu Huang,
• Xu-Dong Wang,
• Yu-Fei Ao,
• Qi-Qiang Wang and
• De-Xian Wang

Beilstein J. Org. Chem. 2025, 21, 884–889, doi:10.3762/bjoc.21.72

• selectivity for heptanedioate (C72−) was attributed to cooperative hydrogen bonding, anion–π interactions, and a size-matching effect, as supported by DFT optimizations. Keywords: anion–π interactions; anion recognition; hydrogen bonding; dicarboxylates; ultracycles; Introduction Macrocycles containing more

• dicarboxylates interact with each subcavity of B4aH through their terminal anionic groups, utilizing cooperative hydrogen bonding and anion–π interactions. The optimal size matching between dicarboxylate and the host cavity, as seen with C72−, enhances the synergistic effect between the two subcavities

• , which relies on solely anion–π interactions, showed weak binding affinity for C62− (Figure S11 in Supporting Information File 1). This underscores the importance of cooperative hydrogen bonding and anion–π interactions for the efficient dicarboxylate binding. To visualize the proposed synergistic

Anion–π catalysis on carbon allotropes

• M. Ángeles Gutiérrez López,
• Mei-Ling Tan,
• Giacomo Renno,
• Augustina Jozeliūnaitė,
• J. Jonathan Nué-Martinez,
• Javier Lopez-Andarias,
• Naomi Sakai and
• Stefan Matile

Beilstein J. Org. Chem. 2023, 19, 1881–1894, doi:10.3762/bjoc.19.140

• , stands for the stabilization of anionic transition states on π-acidic aromatic surfaces. Anion–π catalysis on carbon allotropes is particularly attractive because high polarizability promises access to really strong anion–π interactions. With these expectations, anion–π catalysis on fullerenes has been

• . Currently, anion–π catalysis on carbon allotropes gains momentum because the combination with electric-field-assisted catalysis promises transformative impact on organic synthesis. Keywords: anion–π interactions; autocatalysis; catalysis; carbon nanotubes; Diels–Alder reactions; electric-field-induced

• than intrinsic anion–π interactions should provide access to really strong catalysts [3]. They have been predicted theoretically to occur on π-stacks [6], and confirmed recently to exist and apply to anion–π catalysis on π-stacked foldamers (Figure 1B) [7] and micelles [8]. However, due to their unique

Synthetic reactions driven by electron-donor–acceptor (EDA) complexes

• Zhonglie Yang,
• Yutong Liu,
• Kun Cao,
• Xiaobin Zhang,
• Hezhong Jiang and
• Jiahong Li

Beilstein J. Org. Chem. 2021, 17, 771–799, doi:10.3762/bjoc.17.67

• with N-aryloxyamides, driven by noncovalent anion–π interactions, which has been described for the first time in a light-promoted process. The construction of C–P bonds Many compounds contain phosphorus, which has gained a high degree of interest in materials, agriculture, medical science, and biology

1,2,3-Triazolium macrocycles in supramolecular chemistry

• Mastaneh Safarnejad Shad,
• Pulikkal Veettil Santhini and
• Wim Dehaen

Beilstein J. Org. Chem. 2019, 15, 2142–2155, doi:10.3762/bjoc.15.211

• -triazole units to more electrophilic 1,2,3-triazolium units by influencing both hydrogen bonding-like and anion–π interactions. Moreover, halogen bond (XB) and chalcogen bond (ChB) interactions (see Figure 1) also been applied for the selective detection of anions by exchanging C5–H protons with halogens

• in the literature in which they bind to the anionic species by utilizing multiple noncovalent interactions based on electrostatics, including hydrogen bonding (HB), anion–π interactions [30], and on Lewis acidity/basicity [31]. 2.1. Bile acid-based 1,2,3-triazolium macrocycles Bile acid-based

• between anions and the NDI motif [59]. NDI was chosen due to its excellent photochemical and electrochemical properties. In addition, the electron deficiency and aromatic nature of NDI is important for anion–π interactions [60] to control the charge-transfer properties. It also has been observed that in

Synthesis and anion binding properties of phthalimide-containing corona[6]arenes

• Meng-Di Gu,
• Yao Lu and
• Mei-Xiang Wang

Beilstein J. Org. Chem. 2019, 15, 1976–1983, doi:10.3762/bjoc.15.193

• noncovalent interactions between anions and the tetrazine rings. Keywords: anion–π interactions; coronarenes; host–guest complexation; N-functionalized phthalimides; O6-corona[3]arene[3]tetrazines; Introduction Synthetic macrocycles [1][2] are always attractive and important because they are unique

Fluorescent hexaaryl- and hexa-heteroaryl[3]radialenes: Synthesis, structures, and properties

• Antonio Avellaneda,
• Courtney A. Hollis,
• Xin He and
• Christopher J. Sumby

Beilstein J. Org. Chem. 2012, 8, 71–80, doi:10.3762/bjoc.8.7

• bladed propeller conformation in solution. Compound 3 is considerably more electron deficient than previously reported hexaaryl[3]radialenes, with reduction potentials of −0.06 and −0.45 V in CH2Cl2. The compounds mostly display red fluorescence with large Stokes shifts. Keywords: anion–π interactions

• tetradentate bridge [18][19]. Hexa(4-pyridyl)[3]radialene also acts as a bridging ligand in a 3-D coordination polymer with AgClO4 [20], while isomorphous 6,3-connected 2-D coordination polymers were obtained when hexakis(4-cyanophenyl)[3]radialene was reacted with AgPF6 and AgClO4 [21]. Anion–π interactions

• have recently received much attention [22][23][24][25][26], where the π-system is typically an electron deficient heterocyclic system. The electron deficient nature of the hexaaryl[3]radialenes is borne out in structures of these compounds which also show anion–π interactions and CH···Xanion hydrogen

Anion–π interactions influence pK_a values

• Christopher J. Cadman and
• Anna K. Croft

Beilstein J. Org. Chem. 2011, 7, 320–328, doi:10.3762/bjoc.7.42

• analysis. Contributions to the relative pKa' values have been interpreted, using M06-2X DFT calculations, as consisting of two components: A small contribution from initial OH–π bonding in the starting materials and a larger contribution from anion–π interactions in the products. Such effects have

• fashion, CH–π interactions and anion–π interactions have been identified as influencing binding in a number of systems. Since key computational investigations have indicated that anion–π interactions might be very important [2][3][4], which is also supported by strong circumstantial evidence from crystal

• -structure mining [5][6][7], there has been a resurgence of work in this area. One prime focus has been on anion–π interactions as a means to design selective supramolecular anion receptors and template-directed synthesis of macrocyclic complexes has also been achieved [8][9][10][11][12][13][14][15][16][17