Deuterated reagents in multicomponent reactions to afford deuterium-labeled products

• Kevin Schofield,
• Shayna Maddern,
• Yueteng Zhang,
• Grace E. Mastin,
• Rachel Knight,
• Wei Wang,
• James Galligan and
• Christopher Hulme

Beilstein J. Org. Chem. 2024, 20, 2270–2279, doi:10.3762/bjoc.20.195

• . Optimization of deuterated Leuckart–Wallach reactiona. Microsomal stability package of deuterated and non-deuterated dihydropyridines. Supporting Information Supporting Information File 86: Experimental and analytical data and copies of NMR spectra. Acknowledgements We thank the UA mass spectrometry and NMR

gem-Difluorination of carbon–carbon triple bonds using Brønsted acid/Bu₄NBF₄ or electrogenerated acid

• Mizuki Yamaguchi,
• Hiroki Shimao,
• Kengo Hamasaki,
• Keiji Nishiwaki,
• Shigenori Kashimura and
• Kouichi Matsumoto

Beilstein J. Org. Chem. 2024, 20, 2261–2269, doi:10.3762/bjoc.20.194

• (NMR) yield, in which trifluorotoluene (CF3C6H5) was used as an internal standard. The use of Tf2NH (5 equiv or 10 equiv) and Bu4NBF4 (5 equiv) in CH2Cl2 at room temperature gave the corresponding product 2a in up to 83% yield (Table 1, entries 1–5). The use of CF3COOH did not yield 2a at all (Table 1

• in the presence of the substrate. The total electricity of 3.0 F/mol vs 1a was passed to the solution. Interestingly, the result gave the corresponding difluorinated compound 2a in 29% yield in the case of 8 mA, as shown by 19F NMR analysis. In addition, 2a was obtained in 42% yield by 19F NMR

• oxidation of method B was conducted by using 8 mA. The reaction of but-3-yn-1-ylbenzene (1b) in method A gave the corresponding compound 2b in 21% isolated yield (Table 2, entry 1). The 19F NMR result indicated 63% yield. Because of the low molecular weight of 2b, the isolated yield might be somewhat lower

Synthesis and reactivity of the di(9-anthryl)methyl radical

• Tomohiko Nishiuchi,
• Kazuma Takahashi,
• Yuta Makihara and
• Takashi Kubo

Beilstein J. Org. Chem. 2024, 20, 2254–2260, doi:10.3762/bjoc.20.193

• , indicating that the high reactivity of the central sp2 carbon. To evaluate the decomposition pathway, the decomposed materials were characterized. Surprisingly, the major compound detected by 1H NMR measurement of the crude material was compound 1, along with di(10-mesityl-9-anthryl)methane (4) as a minor

• O–O bond cleavage to give compounds 1 and 5 (Scheme 2). Owing to the high reactivity of the DAntM radical, cyclic voltammogram (CV) was measured by using the stable DAntM cation, prepared from compound 3 oxidized by antimony(V) chloride, which can be characterized by 1H, 13C NMR, and UV–vis

• . Decomposition pathway of the DAntM radical under air conditions. Supporting Information Supporting Information File 81: Synthetic procedure and compound characterization data (1H, 13C NMR, MS, melting point, X-ray crystallography) of new compounds. DFT calculation results and optimized structural Cartesian

Metal-free double azide addition to strained alkynes of an octadehydrodibenzo[12]annulene derivative with electron-withdrawing substituents

• Naoki Takeda,
• Shuichi Akasaka,
• Susumu Kawauchi and
• Tsuyoshi Michinobu

Beilstein J. Org. Chem. 2024, 20, 2234–2241, doi:10.3762/bjoc.20.191

• indicates that the formed double azide adduct is 6a, which is consistent with our previous report [18]. The double azide addition was further investigated by changing the reaction temperature. The rate constant was determined by the temperature-dependent 1H NMR spectra in CDCl3. The reaction kinetics

• previously reported electron-donating hexyloxy substituents. The addition pattern was experimentally investigated by 2D NMR, which was also supported by DFT calculations. The bistriazole product displayed fluorescence in the visible range with a fluorescence quantum yield of 7.0%. Finally, the developed

• partially azidated poly(vinyl chloride) (PVA-N3) was prepared by stirring poly(vinyl chloride) and NaN3 in DMF at room temperature overnight. Measurements NMR spectra were recorded using a JEOL mode Al300 (300 MHz) at room temperature. Deuterated chloroform was used as the solvent unless otherwise stated

Selective hydrolysis of α-oxo ketene N,S-acetals in water: switchable aqueous synthesis of β-keto thioesters and β-keto amides

• Haifeng Yu,
• Wanting Zhang,
• Xuejing Cui,
• Zida Liu,
• Xifu Zhang and
• Xiaobo Zhao

Beilstein J. Org. Chem. 2024, 20, 2225–2233, doi:10.3762/bjoc.20.190

• by other acids such as H2SO4 and CF3SO3H, the reaction showed poor effectiveness due to the poor solubility of 1a in water (Table 1, entries 4 and 5). Most notably, 2a was an inseparable mixture of keto and enol isomers, reaching a keto/enol ratio of 5:4 as determined by 1H NMR spectroscopy. Thus

• thioesters and β-keto amides by simply changing reaction conditions. These features, including a good substrate scope, excellent yield and selectivity and ease of scale-up, rendered the green hydrolysis reaction very environment-friendly, practical, and attractive. Experimental 1H and 13C{1H} NMR spectra

• . Reaction conditions A: 1 (0.25 mmol), DBSA (87.9 mg, 0.25 mmol), H2O (1 mL), reflux, 5 h. Isolated yield is stated. Keto/enol ratio of 2 was determined by 1H NMR spectroscopy. Synthesis of β-keto amides 3. Reaction conditions B: 1 (0.25 mmol), NaOH (0.75 mmol, 30 mg), H2O (1 mL), reflux, 24 h. Isolated

Electrochemical allylations in a deep eutectic solvent

• Sophia Taylor and
• Scott T. Handy

Beilstein J. Org. Chem. 2024, 20, 2217–2224, doi:10.3762/bjoc.20.189

• partial solubility of ethylene glycol in methoxycyclopentane as ethylene glycol could be clearly seen in the 1H NMR spectrum of the crude reaction extracts. It should also be noted that the lower isolated yields most likely reflect mechanical losses during extraction and chromatographic separation as the

• funnel with the aid of 10 mL of deionized (DI) water followed by 20 mL of diethyl ether. The organic layer was separated, dried with anhydrous magnesium sulfate, filtered, and the solvent removed in vacuo to afford the crude product, which was first analyzed by 1H NMR spectroscopy and then purified using

• sulfate, filtered, and the solvent removed in vacuo to afford the crude product, which was first analyzed by 1H NMR spectroscopy and then purified using flash column chromatography. The graphite electrodes were not polished in between reactions, but were rinsed with DI water and then acetone. General Sn

Heterocycle-guided synthesis of m-hetarylanilines via three-component benzannulation

• Andrey R. Galeev,
• Maksim V. Dmitriev,
• Alexander S. Novikov and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2024, 20, 2208–2216, doi:10.3762/bjoc.20.188

• reaction was expected, Figure 2) with morpholine under previously found conditions (Scheme 2). To our delight, the meta-1,2,4-oxadiazole aniline 3ab, formed by the sequence of aldol-type reactions, was isolated in 80% yield and its structure was confirmed by NMR and single crystal X-ray analysis (CCDC

• data of new compounds and NMR spectra. Supporting Information File 64: xyz files with Cartesian atomic coordinates for all model structures and CIF-files for compounds 1g, 3ab, 3bb and 3ca. Funding This study was performed under financial support of the Ministry of Science and Higher Education of the

Natural resorcylic lactones derived from alternariol

• Joachim Podlech

Beilstein J. Org. Chem. 2024, 20, 2171–2207, doi:10.3762/bjoc.20.187

• : Total synthesis and comparison of the NMR spectra revealed that this natural product is identical with altertenuol [41], whose structure was correctly given previously [42]. Furthermore, the originally proposed structures [43] of graphislactones E and F were corrected after total synthesis and

• comparison of NMR spectra [44]. Occasionally, natural products have been reported more than one time as new compounds and were given several names. Only the first given name should be used and further names are thus obsolete: Verrulactone D is erroneously given in the SciFinder database as synonym for

• from an unidentified endophytic fungus [124] and later from colletotrichum sp. [125], Lachnum abnorme [126], Diaporthe phragmitis [127] and a further D. sp. [128], and deviantly from the flower buds of the banana species Musa nana [129]. Its structure was determined by NMR spectroscopy [126] and

Novel truxene-based dipyrromethanes (DPMs): synthesis, spectroscopic characterization and photophysical properties

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2024, 20, 2163–2170, doi:10.3762/bjoc.20.186

• purified through silica-gel column chromatography. After successfully synthesizing these easy-to-make yet interesting molecules, they were fully characterized by means of the standard spectroscopic techniques (1H NMR, 13C NMR and HRMS). We are of the opinion that these truxene-based systems will be useful

• derivatives were successfully characterized and their structures were established by means of the 1H and 13C NMR spectroscopy, besides further confirmation by mass spectrometry (see Supporting Information File 1). The UV–vis absorption, emission and time-resolved fluorescence spectra Emission and absorption

• like 1H NMR, 13C NMR, and mass spectral data. The preliminary UV–vis absorption as well as fluorescence emission spectral data for thus prepared truxene-based compounds were recorded in chloroform and compared as well. Additionally, time-resolved fluorescence lifetime decays were also measured for thus

O,S,Se-containing Biginelli products based on cyclic β-ketosulfone and their postfunctionalization

• Kateryna V. Dil and
• Vitalii A. Palchykov

Beilstein J. Org. Chem. 2024, 20, 2143–2151, doi:10.3762/bjoc.20.184

• in our study (Table 1, entries 1–6), but in any case, we received a mixture of regioisomeric products 2a/2a’ (3:1 to 2:1) confirmed by 2D NMR spectroscopy (see Supporting Information File 1, Figures S1–S6). Classical conditions for Biginelli reaction (reflux in ethanolic HCl) gave only 23% yield

• ]. We hope that compound 2r and its analogues obtained in this work can be further deeply studied by in silico and in vitro methods to discover the compound most suitable for clinical trials. The structures of the synthesized compounds 2a–r were confirmed by spectral data. The 1H NMR spectra of the

• signals clearly corresponds to the heterocycles depicted above. Figure S8 (see Supporting Information File 1) shows 1H NMR spectra for Ph-substituted O,S,Se-DHPMs 2a,h,o. It can be seen from them that when going from oxygen to selenium (2h→2a→2o), the signals of both NH groups shift to down field (7.87

Efficacy of radical reactions of isocyanides with heteroatom radicals in organic synthesis

• Akiya Ogawa and
• Yuki Yamamoto

Beilstein J. Org. Chem. 2024, 20, 2114–2128, doi:10.3762/bjoc.20.182

• . Because of this conjugation, the aromatic ring at the N of the 1,1-addition product 4 (R = Ar, E = PhS) geometrically isomerizes faster than the NMR timescale, so that the two thio groups of 4 are observed to be equivalent in NMR spectroscopy. In the case of diphenyl diselenide as a representative organic

From perfluoroalkyl aryl sulfoxides to ortho thioethers

• Yang Li,
• Guillaume Dagousset,
• Emmanuel Magnier and
• Bruce Pégot

Beilstein J. Org. Chem. 2024, 20, 2108–2113, doi:10.3762/bjoc.20.181

• decided to use 2 equivalents of DIPEA at low temperature. After ten minutes at −15 °C to allow for the reaction between phenyl trifluoromethyl sulfoxide (1a) and acetonitrile, the base was added and the reaction was stirred for the same amount of time. To our delight, a good NMR yield of 74% was received

• 1h–j proved also efficient for this rearrangement giving rise to the corresponding thioethers 2h–j in good NMR yields and lower isolated yield in the case of the more volatile adduct 2i. Finally, trifluoromethyl selenoxide 1k was tested as a substrate, and the rearranged product was obtained in a low

• equiv) was slowly added to the flask with a syringe and the reaction was stirred for another 10 min. At the end of the reaction, 1 mL of chloroform and a known amount of trifluoromethoxybenzene were added to the flask in order to determine the 19F NMR yield. To purify the product, the reaction mixture

Computational toolbox for the analysis of protein–glycan interactions

• Ferran Nieto-Fabregat,
• Maria Pia Lenza,
• Angela Marseglia,
• Cristina Di Carluccio,
• Antonio Molinaro,
• Alba Silipo and
• Roberta Marchetti

Beilstein J. Org. Chem. 2024, 20, 2084–2107, doi:10.3762/bjoc.20.180

• needed to deeply investigate the multifaceted aspects of protein–glycan interactions. To date, advanced and versatile NMR, X-ray crystallography, and MS methods [36][37][38] above all, have been developed to reach extensive information on the structural and conformational features of glycans and proteins

• publicly accessible platform for multiple glycoinformatic studies and web tools, which among the other services allows the users to locate adiabatic maps for specific glycosidic linkages. Generally, CSDB offers a wealth of valuable features; it provides structural, bibliographic, taxonomic, NMR

• , keywords, biological source data up to strains, methods used to elucidate structures, NMR signal assignment and other information (http://csdb.glycoscience.ru/database/). 2. Disac3DB: free annotated database that contains the 3D structural information of about 120 entries of disaccharides. For each

Diastereoselective synthesis of highly substituted cyclohexanones and tetrahydrochromene-4-ones via conjugate addition of curcumins to arylidenemalonates

• Deepa Nair,
• Abhishek Tiwari,
• Banamali Laha and
• Irishi N. N. Namboothiri

Beilstein J. Org. Chem. 2024, 20, 2016–2023, doi:10.3762/bjoc.20.177

• undergoing yet another diastereoselective 6-endo-trig intramolecular oxa-Michael addition. The structure and stereochemistry of compounds 3 and 4 were confirmed by 1H-1H-COSY and 1H-1H-NOESY NMR experiments. This was further unambiguously established by single crystal X-ray analysis of a representative

• . Reaction optimisation using phase-transfer catalysts.a Scope of alkylidenemalonates and curcumins.a Supporting Information Supporting Information File 38: Experimental procedures and characterization data. Supporting Information File 39: Copies of NMR spectra of all new compounds. Supporting Information

Understanding X-ray-induced isomerisation in photoswitchable surfactant assemblies

• Beatrice E. Jones,
• Camille Blayo,
• Jake L. Greenfield,
• Matthew J. Fuchter,
• Nathan Cowieson and
• Rachel C. Evans

Beilstein J. Org. Chem. 2024, 20, 2005–2015, doi:10.3762/bjoc.20.176

• the samples ex-situ for 3.5 hours to achieve a Z-rich PSS, where the percentage isomerised has been determined previously using 1H NMR spectroscopy [20]. The 10 wt % sample was measured over 800 X-ray exposures of 250 ms each. The initial Z-rich PSS SAXS pattern shows a strong interaction peak at Q

• ± 4% E-to-Z isomerisation for 10 and 90 wt % AAPTAB, respectively, as determined previously using 1H NMR [20]. SAXS SAXS measurements were performed at the high-throughput SAXS beamline B21, Diamond Light Source (Oxfordshire, UK) [47]. The X-ray beam energy was 13.0 keV and the detector distance set

Allostreptopyrroles A–E, β-alkylpyrrole derivatives from an actinomycete Allostreptomyces sp. RD068384

• Marwa Elsbaey,
• Naoya Oku,
• Mohamed S. A. Abdel-Mottaleb and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2024, 20, 1981–1987, doi:10.3762/bjoc.20.174

• structures were elucidated by 1D and 2D NMR spectroscopic analyses, HRESIMS, and chemical derivatization. The absolute configurations of compounds 2 and 3 were predicted by comparison of experimental and calculated specific rotation data. Compounds 1–5 are the first examples of natural pyrroles substituted

• . Analysis of 1H NMR, 13C NMR (Table 1), and HSQC spectra revealed a formyl group (δC 186.3/δH 9.89), an olefinic methine (δC 131.1/δH 7.64), an acyl carbonyl carbon (δC 163.3), three non-protonated olefinic carbons (δC 133.4, 126.4, and 123.1), a deshielded non-protonated sp3 carbon (δC 70.1), six sp3

• HRESITOFMS and NMR analytical data (Table 2), inferring that compounds 2 and 3 were isomers of 1. In fact, their NMR spectra were closely similar to those for 1 except a little difference in the alkyl side chain terminus. In a COSY spectrum of 2, the terminal doublet methyl proton was correlated with an

Development of a flow photochemical process for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence: in situ-generated 2-benzopyrylium as photoredox catalyst and reactive intermediate

• Masahiro Terada,
• Zen Iwasaki,
• Ryohei Yazaki,
• Shigenobu Umemiya and
• Jun Kikuchi

Beilstein J. Org. Chem. 2024, 20, 1973–1980, doi:10.3762/bjoc.20.173

• , experimental procedures, and characterization data. Supporting Information File 30: Copies of NMR spectra. Funding This work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Hybrid Catalysis for Enabling Molecular Synthesis on Demand” (JP17H06447) and a Grant-in-Aid for

Radical reactivity of antiaromatic Ni(II) norcorroles with azo radical initiators

• Siham Asyiqin Shafie,
• Ryo Nozawa,
• Hideaki Takano and
• Hiroshi Shinokubo

Beilstein J. Org. Chem. 2024, 20, 1967–1972, doi:10.3762/bjoc.20.172

• analysis, which revealed that two alkyl substituents were located on the same side of the molecule (Figure 2a). Compared to the planar structure of 1 (Figure 2b) [2], 2a displays a nonplanar structure due to the sp3 carbon atoms adjacent to the nitrogen atoms. The 1H NMR spectrum of 2a confirmed that the

• . Supporting Information Supporting Information File 26: Experimental procedures, compound characterization data including NMR and MS spectra, additional crystal data and details from DFT calculations. Funding This work was supported by Japan Society for the Promotion of Science (JSPS) KAKENHI grants

1,2-Difluoroethylene (HFO-1132): synthesis and chemistry

• Liubov V. Sokolenko,
• Taras M. Sokolenko and
• Yurii L. Yagupolskii

Beilstein J. Org. Chem. 2024, 20, 1955–1966, doi:10.3762/bjoc.20.171

• ], respectively, while reference [68] provides UV-spectral data of both isomers. 1H, 19F, and 13C NMR data [69][70] are given in Table 2. Chemistry of HFO-1132 Isomerization Iodine-catalyzed cis–trans isomerization of 1,2-difluoroethylene and corresponding equilibrium measurements were described in the 1960s [47

• ]. Additionally, when the reaction was performed using DMSO-d6 (or CD3CN) and CH3ONa, H/D exchange occurred already at ambient temperature (25 °C, 20 h) [78]. The formation of CDF=CDF was confirmed by NMR spectroscopy, namely by the change of signal multiplicity in the 19F NMR spectra of E- and Z-isomers of 1,2

• -difluoroethylene and the disappearance of vinyl protons resonances in the 1H NMR spectra [78]. Addition to the C=C bond Halogen addition: 1,2-Difluoroethylene was reported to react with chlorine [46][79] and bromine [51] under irradiation, yielding 1,2-difluoro-1,2-dihaloethanes in moderate to high yield (Scheme 9

Regioselective alkylation of a versatile indazole: Electrophile scope and mechanistic insights from density functional theory calculations

• Pengcheng Lu,
• Luis Juarez,
• Paul A. Wiget,
• Weihe Zhang,
• Krishnan Raman and
• Pravin L. Kotian

Beilstein J. Org. Chem. 2024, 20, 1940–1954, doi:10.3762/bjoc.20.170

• Scheme 1 compound 6 was treated with isopropyl iodide (7) in DMF in the presence of sodium hydride to provide products 8 and 9 in 38% and 46% yields, respectively. The structures of both compounds were unambiguously assigned using X-ray crystallography and 1H and nuclear Overhauser effect (NOE) NMR

• moisture-sensitive reagents were performed under a nitrogen or argon atmosphere. Silica gel chromatography was performed using prepacked silica gel columns (RediSep® Rf, Teledyne ISCO). An aluminum block atop a hotplate with a thermocouple was used to heat reactions to the specified temperatures. NMR

• purified by chromatography (silica [24 g], eluting with EtOAc in hexane from 0–70%) to give methyl 5-bromo-1-alkyl-1H-indazole-3-carboxylate, in 90–98%. For 15a, 284.5 mg, 90%, as a white solid. Mp 141.3 °C; 1H NMR (300 MHz, DMSO-d6) δ 8.19 (dd, J = 1.9, 0.7 Hz, 1H), 7.82 (dd, J = 9.0, 0.7 Hz, 1H), 7.65

A new platform for the synthesis of diketopyrrolopyrrole derivatives via nucleophilic aromatic substitution reactions

• Vitor A. S. Almodovar and
• Augusto C. Tomé

Beilstein J. Org. Chem. 2024, 20, 1933–1939, doi:10.3762/bjoc.20.169

• than the oxygen due to the preferential existence of 4-hydroxypyridine in the pyridin-4-one tautomeric form [37][38][39]. The structures of dyes 3a–f, 4a, 4d and 4f were unambiguously established through their 1H, 13C and 19F NMR and mass spectra. The 1H NMR spectra of the symmetrical compounds

• the protons of the N–CH2C6F5 and N–CH2C6F4XR groups, respectively. All 19F NMR spectra confirmed the selective substitution of the 4-fluorine atoms (in one or in two rings) by the disappearance of the signal corresponding to the resonance of those atoms. Mass spectra of compounds 3a–f, 4a, 4d and 4f

• apparatus. NMR spectra were recorded on a Bruker DRX 300 Avance operating at 300.13 MHz (for 1H NMR), at 75.47 MHz (for 13C NMR) and 282 MHz (for 19F NMR). Deuterated chloroform (CDCl3) was used as the solvent and tetramethylsilane (TMS) as the internal reference. The chemical shifts (δ) are expressed in

Negishi-coupling-enabled synthesis of α-heteroaryl-α-amino acid building blocks for DNA-encoded chemical library applications

• Matteo Gasparetto,
• Balázs Fődi and
• Gellért Sipos

Beilstein J. Org. Chem. 2024, 20, 1922–1932, doi:10.3762/bjoc.20.168

• each reaction (Supporting Information File 1). Supporting Information Supporting Information File 14: Experimental part and NMR spectra. Acknowledgements The authors thank Dr. Attila Sveiczer and Dr. Mounir Raji for the consultations and technical support during the practical work of the project, and

Novel oxidative routes to N-arylpyridoindazolium salts

• Oleg A. Levitskiy,
• Yuri K. Grishin and
• Tatiana V. Magdesieva

Beilstein J. Org. Chem. 2024, 20, 1906–1913, doi:10.3762/bjoc.20.166

• -arylpyridoindazolium salts S1–S3 was confirmed with HRMS and 1H, 13C and 19F NMR data; the complete assignment of the signals was performed using 2D NMR methods. The N–N bond formation was additionally confirmed via comparison of the 1H spectra for the salts and their diarylamine precursors. The absence of the signals

• corresponding diaryl amines A1–A3 (). Supporting Information Supporting Information File 8: Analytical data, NMR and MS spectra. Funding This work was supported by Russian Science Foundation (Project number 22-73-00040). The NMR part of this work was supported by M. V. Lomonosov Moscow State University

Electrochemical radical cation aza-Wacker cyclizations

• Sota Adachi and
• Yohei Okada

Beilstein J. Org. Chem. 2024, 20, 1900–1905, doi:10.3762/bjoc.20.165

• with stirring. The solution was diluted with water and extracted with dichloromethane. The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. Yields were determined by 1H NMR analysis using benzaldehyde as an internal standard (Table 1). Silica gel column

• cyclization.a Supporting Information Supporting Information File 6: General remarks and characterization data, including copies of 1H and 13C NMR spectra. Funding This work was supported in part by JSPS KAKENHI Grant No. 22K05450 (to Y. O.), and TEPCO Memorial Foundation (to Y. O.).

Access to 2-oxoazetidine-3-carboxylic acid derivatives via thermal microwave-assisted Wolff rearrangement of 3-diazotetramic acids in the presence of nucleophiles

• Ivan Lyutin,
• Vasilisa Krivovicheva,
• Grigory Kantin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2024, 20, 1894–1899, doi:10.3762/bjoc.20.164

• information, X-ray crystallographic data, synthetic procedures, analytical data and NMR spectra for the reported compounds. Acknowledgements We thank the Research Center for Magnetic Resonance, the Center for Chemical Analysis and Materials Research, and the Center for X-ray Diffraction Methods of Saint