A comparison of structure, bonding and non-covalent interactions of aryl halide and diarylhalonium halogen-bond donors

• Nicole Javaly,
• Theresa M. McCormick and
• David R. Stuart

Beilstein J. Org. Chem. 2024, 20, 1428–1435, doi:10.3762/bjoc.20.125

• compounds (Scheme 1b) [21]. The amount of s-character in the orbital used by the central atom (both chalcogen and halogen) to bond with the aryl groups decreases moving down the respective group (16 and 17) [21]. We also found with a limited set of six compounds that the association constant (Ka) for the

Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

• -trinitrofluorenone (TNF) with a good association constant of 2100 M−1. Upon protonation of the pyrimidine nitrogen atom the hydrogen bond is disturbed, which should result in a conformational change to an open W-shaped form. Even though an acid-mediated hydrogen bond disruption was expected, no clear experimental

Enhanced host–guest interaction between [10]cycloparaphenylene ([10]CPP) and [5]CPP by cationic charges

• Eiichi Kayahara,
• Yoshiyuki Mizuhata and
• Shigeru Yamago

Beilstein J. Org. Chem. 2024, 20, 436–444, doi:10.3762/bjoc.20.38

• , [10]CPP⊃[5]CPP2+. While the same host–guest complex consisted of neutral CPPs, [10]CPP⊃[5]CPP, was already reported, the cationic complex showed an about 20 times higher association constant in (CDCl2)2 at 25 °C (103 mol L−1). Electrochemical and photophysical analyses and theoretical calculations

• suggested the partial electron transfer from [10]CPP to [5]CPP2+ in the complex, and this charge-transfer (CT) interaction is most likely the origin of the higher association constant of the dicationic complex than the neutral one. Keywords: charge-transfer; cycloparaphenylene; dication; host–guest

• state of the corresponding host–guest complex. Here, we report on the size complementary formation of the host–guest complex between [10]CPP and the dication of [5]CPP, [10]CPP⊃[5]CPP2+ (Figure 1c). The association constant, Ka, determined by 1H NMR titration, was about 20 times higher than that of the

A fluorescent probe for detection of Hg²⁺ ions constructed by tetramethyl cucurbit[6]uril and 1,2-bis(4-pyridyl)ethene

• Xiaoqian Chen,
• Naqin Yang,
• Yue Ma,
• Xinan Yang and
• Peihua Ma

Beilstein J. Org. Chem. 2023, 19, 864–872, doi:10.3762/bjoc.19.63

• that TMeQ[6] and G form an inclusion complex with a host–guest ratio of 1:1 and the equilibrium association constant (Ka) was 2.494 × 104 M−1. The G@TMeQ[6] fluorescent probe can sensitively recognize Hg2+ ions by fluorescence enhancement. The linear range is 0.33 × 10−5–1.65 × 10−5 mol·L−1, R2

• that a G and TMeQ[6] inclusion complex is formed with a 1:1 stoichiometry. Isothermal titration calorimetry (ITC) analysis The association constant and thermodynamic parameters of the host–guest interaction between G and TMeQ[6] can be obtained using ITC. At 25 °C, a neutral aqueous solution of TMeQ[6

• ] (1.0 × 10−4 mol·L−1, 1.00 mL) was gradually added to the aqueous solution of G, and the exothermic isotherms (Figure S1 in Supporting Information File 1) and thermodynamic data (Table 1) were obtained. The equilibrium association constant (Ka) of G and TMeQ[6] is 2.494 × 104 M−1, ΔH = −88.43 kJ/mol

Phenanthridine–pyrene conjugates as fluorescent probes for DNA/RNA and an inactive mutant of dipeptidyl peptidase enzyme

• Josipa Matić,
• Tana Tandarić,
• Marijana Radić Stojković,
• Filip Šupljika,
• Zrinka Karačić,
• Ana Tomašić Paić,
• Lucija Horvat,
• Robert Vianello and
• Lidija-Marija Tumir

Beilstein J. Org. Chem. 2023, 19, 550–565, doi:10.3762/bjoc.19.40

• increased upon addition of the enzyme (Figure 6), suggesting the important role of the hydrophobic pyrene subunit for protein binding [18]. Association constant and thermodynamical binding parameters were additionally determined by ITC titrations [17]. The resulting titration data were fitted to a single

• Scatchard equation [38] and Global Fit procedure [40]. Calculations mostly gave values of ratio n = 0.2 ± 0.05, but for easier comparison all Ka values were re-calculated for fixed n = 0.2. Values for Ka have satisfactory correlation coefficients (>0.98). In Scatchard equation values of association constant

Synthesis of a new water-soluble hexacarboxylated tribenzotriquinacene derivative and its competitive host–guest interaction for drug delivery

• Man-Ping Li,
• Nan Yang and
• Wen-Rong Xu

Beilstein J. Org. Chem. 2022, 18, 539–548, doi:10.3762/bjoc.18.56

• association constant was determined to be Ka = (7.67 ± 0.34) × 104 M−1 by nonlinear curve fitting [33] (Figure 1d). Host–guest complexation of TBTQ-CB6 with doxorubicin (DOX). The host–guest complexation between TBTQ-CB6 and DOX was studied by methods similar to those used for TBTQ-CB6 and MV. The 1H NMR

BINOL as a chiral element in mechanically interlocked molecules

• Matthias Krajnc and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2022, 18, 508–523, doi:10.3762/bjoc.18.53

• macrocycle (S)-61-Me22+. Only the first association constant (K11) is given. aIn acetone-d6/D2O 98:2. bIn acetone-d6/D2O 99:1. Synthesis of Beer´s [3]rotaxane (S)-68. Association constants of different anions (used as the Bu4N+-salts) to the [2]rotaxane (S)-68 and axle (S)-65. Only the first association

• constant (K11) is given. aIn CHCl3/CH3OH/H2O 60:39:1. bComplex equlibria, no association constant determined. Funding Funding from the DFG (Sachbeihilfe NI1273/2-2 and Heisenberg-Professorship to J.N., NI1273/4-1) is gratefully acknowledged.

Tetraphenylethylene-embedded pillar[5]arene-based orthogonal self-assembly for efficient photocatalysis in water

• Zhihang Bai,
• Krishnasamy Velmurugan,
• Xueqi Tian,
• Minzan Zuo,
• Kaiya Wang and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2022, 18, 429–437, doi:10.3762/bjoc.18.45

• corresponds to a 1:1 binding stoichiometric ratio between G and m-TPEWP5 in the aqueous solution. Furthermore, the association constant (Ka) [36] was calculated to be 8.62 × 104 M−1 based on the UV–vis titration experiment (Figure S4, Supporting Information File 1). This result further confirmed that the

Synthesis of a novel aminobenzene-containing hemicucurbituril and its fluorescence spectral properties with ions

• Qingkai Zeng,
• Qiumeng Long,
• Jihong Lu,
• Li Wang,
• Yuting You,
• Xiaoting Yuan,
• Qianjun Zhang,
• Qingmei Ge,
• Hang Cong and
• Mao Liu

Beilstein J. Org. Chem. 2021, 17, 2840–2847, doi:10.3762/bjoc.17.195

• association constant up to (2.1 ± 0.3) × 104 M−1. Meanwhile, this macrocycle showed no obvious or only slight enhancement of the fluorescence intensity with selected anions. Keywords: amidobenzene-containing macrocycle; hemicucurbituril; host–guest interaction; macrocycle; modification; Introduction

• initially studied. Among the metal cations examined, the fluorescence intensity of macrocycle 4 quenched significantly when adding the corresponding equivalents of Fe3+ and Cu2+. Notably, this macrocyclic host molecule formed 1:1 complexes with Fe3+ in DMF with an association constant up to (2.1 ± 0.3

• constants for 1:1 complexation between the host 4 and the guest cations were calculated by Equation 1 [47], where Ka is the association constant of the host–guest interaction, while ΔI is the change in the fluorescence intensity of the host upon gradual addition of the guest, and Δa refers to the different

Insight into functionalized-macrocycles-guided supramolecular photocatalysis

• Minzan Zuo,
• Krishnasamy Velmurugan,
• Kaiya Wang,
• Xueqi Tian and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2021, 17, 139–155, doi:10.3762/bjoc.17.15

• molecules can absorb light and transfer energy, making the assemblies an efficient light-harvesting system. The host–guest binding stoichiometry is 1:1, and the association constant (Ka) of WP5β-CAR was calculated to be (2.34 ± 2.06) × 105 M−1. This system can function as a photocatalyst for the reduction

Molecular basis for protein–protein interactions

• Brandon Charles Seychell and
• Tobias Beck

Beilstein J. Org. Chem. 2021, 17, 1–10, doi:10.3762/bjoc.17.1

• modelled by the McGhee–von Hippel model of nonspecific protein binding to a surface [86]. In this model, the association with nucleic acids, quantified by KNA, is dependent on the cooperativity coefficient ω, which is based on the protein–protein association constant. A ω value of 1 represents no

Construction of pillar[4]arene[1]quinone–1,10-dibromodecane pseudorotaxanes in solution and in the solid state

• Xinru Sheng,
• Errui Li and
• Feihe Huang

Beilstein J. Org. Chem. 2020, 16, 2954–2959, doi:10.3762/bjoc.16.245

• spectrometry results, we believed that the differences between the stoichiometric ratio of the complexation in the solid state and in solution could be owing to the competitive role of solvent molecules in the combination of H and G. The association constant (Ka) calculated by the nonlinear curve fitting

Recent developments in enantioselective photocatalysis

• Callum Prentice,
• James Morrisson,
• Andrew D. Smith and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2020, 16, 2363–2441, doi:10.3762/bjoc.16.197

• intermediate 196. In 195 there is additional steric repulsion between the large R group and the thioxanthone that is not present in 195’, which results in a smaller association constant and a larger calculated separation between the allene and the chromophore in 195 (r = 510 pm) relative to 195’ (r = 363 pm

[3 + 2] Cycloaddition with photogenerated azomethine ylides in β-cyclodextrin

• Margareta Sohora,
• Leo Mandić and
• Nikola Basarić

Beilstein J. Org. Chem. 2020, 16, 1296–1304, doi:10.3762/bjoc.16.110

• ). However, the approximated association constant for 3@β-CD, K = 2600 ± 600 M−1, is similar to the known association constants for different adamantane derivatives with β-CD (K = 103–105 M−1) [52], in agreement with the anticipated good fit of the adamantane moiety in 3 to the β-CD cavity. After

Preparation of anthracene-based tetraperimidine hexafluorophosphate and selective recognition of chromium(III) ions

• Qing-Xiang Liu,
• Feng Yang,
• Zhi-Xiang Zhao,
• Shao-Cong Yu and
• Yue Ding

Beilstein J. Org. Chem. 2019, 15, 2847–2855, doi:10.3762/bjoc.15.278

• detection (LOD) was calculated to be 2.33⋅10−7 M (Supporting Information File 1, Figure S3). This value is analogous to the lowest corresponding value that has been reported in the literature (9.40⋅10−7–5.55⋅10−6 M) [44][45][46]. The association constant KSV was calculated to be 6.6⋅104 M−1 (R = 0.998) for

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

• changes in the CDCl3 solution of anionic species (Figure 3). The receptor 1a has shown remarkable affinity toward fluoride ion with an association constant of 560 M−1 followed by Cl− > Br− > I− > CH3COO− with the affinity range of 5.6 × 102 to 6.0 × 101 M−1 but no binding was observed with the H2PO4− ion

• association constant of macrocycle 3 in the more competitive 15% water/acetone medium, still demonstrating a high binding affinity for sulfate anion (Ka = 2.5 × 105 M−1) while the cage 3 did not show any binding toward the other tested anions in the more aqueous solvent mixture. 2.3. Redox-active 1,2,3

Multiple threading of a triple-calix[6]arene host

• Veronica Iuliano,
• Roberta Ciao,
• Emanuele Vignola,
• Carmen Talotta,
• Patrizia Iannece,
• Margherita De Rosa,
• Annunziata Soriente,
• Carmine Gaeta and
• Placido Neri

Beilstein J. Org. Chem. 2019, 15, 2092–2104, doi:10.3762/bjoc.15.207

• -tetrachloroethane as internal standard, an apparent association constant of 1.01 ± 0.03 × 104 M−1 was calculated for the 7+6 pseudo[2]rotaxane. When 1 equiv of 7+·TFPB− salt was added to the 1:1 mixture of 6 and 7+·TFPB− in CDCl3 (Figure 4c), then, in addition to the benzylic resonances of the 7+6 pseudo[2]rotaxane

• − δcomplexed = 2.69), −0.88 (Δδ = 2.58), −0.57 (Δδ = 1.94), −0.40 (Δδ = 1.32), and 0.64 ppm (Δδ = 2.37) ppm attributable, respectively, to the β, γ, δ, ε, and α H-atoms of the pentyl chain of axle 4+ inside the calix-cavity of 6 (Figure 7). An apparent association constant of 1.20 ± 0.02 × 104 M–1 was

• (Figure 10) of this mixture confirmed the formation of the 8+6 pseudo[2]rotaxane by the presence of a molecular ion peak at 3408.3230 m/z (calcd 3408.3122 for C233H306NO18+). Finally, an apparent association constant of 5.70 ± 0.03 × 102 M−1 was calculated by 1H qNMR analysis for the single-threaded 8+6

Complexation of 2,6-helic[6]arene and its derivatives with 1,1′-dimethyl-4,4′-bipyridinium salts and protonated 4,4'-bipyridinium salts: an acid–base controllable complexation

• Jing Li,
• Qiang Shi,
• Ying Han and
• Chuan-Feng Chen

Beilstein J. Org. Chem. 2019, 15, 1795–1804, doi:10.3762/bjoc.15.173

• the nonlinear curve-fitting method [40]. As shown in Table 1, compared with its derivatives, the unsubstituted host helic[6]arene H1 showed the strongest complexation with all guests tested. The association constant (Ka) of complex H1·G1 was calculated to be (6.76 ± 1.02) × 103 M−1, while the Ka of H2

2,3-Dibutoxynaphthalene-based tetralactam macrocycles for recognizing precious metal chloride complexes

• Li-Li Wang,
• Yi-Kuan Tu,
• Huan Yao and
• Wei Jiang

Beilstein J. Org. Chem. 2019, 15, 1460–1467, doi:10.3762/bjoc.15.146

• ] or (TBA)2[PdCl4]. Binding constants of 1 to the precious metal chloride complexes were determined in CDCl3 by 1H NMR titrations (Figures S9−S14, Supporting Information File 1). The data are listed in Table 1. TBA[AuCl4] shows the highest association constant (Ka) with a value of 265 ± 33 M−1. The Ka

• mass spectrum (Figure S15, Supporting Information File 1). Therefore, the association constant for (TBA)2[PdCl4] may, in fact, be caused by the mixture of (TBA)2[PdCl4], TBACl, and (TBA)2[Pd2Cl6]. Tetralactam macrocycles are known to bind chloride ions as well [4][40]. Indeed, 1 is able to bind TBACl

Complexation of a guanidinium-modified calixarene with diverse dyes and investigation of the corresponding photophysical response

• Yu-Ying Wang,
• Yong Kong,
• Zhe Zheng,
• Wen-Chao Geng,
• Zi-Yi Zhao,
• Hongwei Sun and
• Dong-Sheng Guo

Beilstein J. Org. Chem. 2019, 15, 1394–1406, doi:10.3762/bjoc.15.139

• according to the Job's plot. The association constant (Ka) was well fitted as 5.0 × 106 M−1 (Table 1) by a 1:1 binding model according to both fluorescence titration and UV–vis titration. The drastically altered fluorescence signal upon complexation, Ifree/Ibound, is calculated as a factor of 37. EY, RB

Synthesis of a water-soluble 2,2′-biphen[4]arene and its efficient complexation and sensitive fluorescence enhancement towards palmatine and berberine

• Xiayang Huang,
• Xinghua Zhang,
• Tianxin Qian,
• Junwei Ma,
• Lei Cui and
• Chunju Li

Beilstein J. Org. Chem. 2018, 14, 2236–2241, doi:10.3762/bjoc.14.198

• exhibited dramatic fluorescence enhancement of more than 600 times upon complexation with 2,2’-CBP4. Particularly, the fluorescence intensity is strong enough to be readily distinguished by the naked eye. Although the two guests have similar structures, the association constant of B with 2,2’-CBP4 (Ka

• presence of 2,2’-CBP4 in aqueous phosphate buffer solution at pH 7.4 at 298 K. The excitation wavelength is at 352.0 nm. Inset: the nonlinear least-squares analysis to calculate the association constant using the fluorescence emission at 530 nm. Visible emission observed from samples of P and B in the

Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules

• Hendrik V. Schröder and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190

• TTFs. However, also the type of substituent on the TTF moiety plays a role in terms of weak secondary binding interactions such as hydrogen bonds [63]. For example TTF 5 which is substituted by ethylene glycol chains displays a high association constant of Ka = 50,000 M−1 in acetonitrile. Additionally

• = 6,300 M−1) which is embedded in an axle molecule with two azide residues. The second station, the dihydroxynaphthalene moiety (green), displays a lower association constant of Ka = 5,800 M−1. The pseudorotaxane precursor was end-capped by a double copper-catalyzed azide–alkyne click reaction in CH2Cl2

• station by hydrogen bonds as shown by the high association constant of a structurally similar pseudorotaxane precursor (Ka = 590,000 M−1). The high association constant is a result of the weakly coordinating anion (WCA) used, i.e., tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. Comparison to a

Calix[6]arene-based atropoisomeric pseudo[2]rotaxanes

• Carmine Gaeta,
• Carmen Talotta and
• Placido Neri

Beilstein J. Org. Chem. 2018, 14, 2112–2124, doi:10.3762/bjoc.14.186

• spectrum of the mixture of 1 and 2+ in CDCl3 remained unchanged after 48 h at 298 K, thus showing that the system had reached the equilibrium condition. At this point, an apparent association constant of 6.2 ± 0.3 × 103 M–1 was calculated by quantitative 1H NMR analysis (tetrachloroethane as internal

• studies. Also in this case, after equilibration at 298 K for 24 h, this preference was reversed in favour of the 3+1cone atropoisomer, with a 3+1cone/3+11,2,3-alt ratio of 8/1. From the equilibrium mixture, an apparent association constant of 9.3 ± 0.4 × 102 M−1 was calculated by quantitative 1H NMR

• analysis (tetrachloroethane as internal standard) for the formation of 3+1cone pseudorotaxane. In a similar way, an apparent association constant of 120 ± 15 M−1 was found for 3+11,2,3-alt pseudorotaxane. As evidenced for axle 2+, also in this case, after the initial formation of the kinetic pseudorotaxane

An amphiphilic pseudo[1]catenane: neutral guest-induced clouding point change

• Tomoki Ogoshi,
• Tomohiro Akutsu and
• Tada-aki Yamagishi

Beilstein J. Org. Chem. 2018, 14, 1937–1943, doi:10.3762/bjoc.14.167

• by 1,4-dicyanobutane. The association constant between the pseudo[1]catenane structure 3 and 1,4-dicyanobutane estimated by 1H NMR at 25 °C was 13.9 M−1 (Supporting Information File 1, Figure S6), which is remarkably lower than the association constant between 1 and 1,4-dicyanobutane (4.6 × 104 M−1

• -dicyanobutane showed two sets of resonances for complexed (Figure 2d, peaks α’ and β’) and uncomplexed 1,4-dicyanobutane (peaks, α and β). The association constant for the host–guest complexes between 1,4-dicyanobutane and 3 at 10 °C was 24.5 M−1, which was calculated from integrations of the complexed

• (Supporting Information File 1, Figure S5, orange peak β’) and uncomplexed signals (Supporting Information File 1, Figure S5, orange peak β) of 1,4-dicyanobutane. The association constant of the complex at 25 °C extrapolated by van 't Hoff plots (Figure S6 in the Supporting Information File 1) was 13.9 M−1

A conformationally adaptive macrocycle: conformational complexity and host–guest chemistry of zorb[4]arene

• Liu-Pan Yang,
• Song-Bo Lu,
• Arto Valkonen,
• Fangfang Pan,
• Kari Rissanen and
• Wei Jiang

Beilstein J. Org. Chem. 2018, 14, 1570–1577, doi:10.3762/bjoc.14.134

• the results are shown in Table 1. Generally, ZB4 shows weaker binding affinities to these guests than TA4 does with the same counterions. For example, ZB4 and cation 3+, with a binding constant of 5.4 × 104 M−1, was the best guest among the studied ones. However, the corresponding association constant

• , Cl, Br, and I, the binding affinities increase with increasing σp. However, the binding affinities decrease with further increasing σp (CF3, NO2, and CN). The guest with iodo substituent (18+) is the best, with an association constant of 4.9 × 105 M−1 at 25 °C. It is interesting to note that although