Single-crystal X-ray Structure Research Articles

Open-Cage Fullerene as Molecular Container for F- , Cl- , Br- and I.

A 19-membered open-cage fullerene derivative was prepared from C60 in 7 steps and 5.5 % yield through the peroxide-mediate pathway. There are four carbonyl groups, an ether oxygen and a quinoxaline moiety on the rim of the orifice. A chloride anion could be inserted into its cavity by heating with hydrochloric acid at 60 °C for 4 h. Encapsulation of fluoride, bromide and iodide anions was also achieved at slightly more forcing conditions, 90 °C for 14 h. Single crystal X-ray structures of the sodium salt of the chloride and the bromide encapsulated derivatives were obtained, which showed the halide anion in the center of the cavity and two sodium cations connecting two cages through coordination to the oxygen atoms on the rim of the orifices. The halide encapsulation ratio is quantitative in the isolated products.

Enzymatic Late-Stage Halogenation of Peptides.

The late-stage site-selective derivatisation of peptides has many potential applications in structure-activity relationship studies and postsynthetic modification or conjugation of bioactive compounds. The development of orthogonal methods for C-H functionalisation is crucial for such peptide derivatisation. Among them, biocatalytic methods are increasingly attracting attention. Tryptophan halogenases emerged as valuable catalysts to functionalise tryptophan (Trp), while direct enzyme-catalysed halogenation of synthetic peptides is yet unprecedented. Here, it is reported that the Trp 6-halogenase Thal accepts a wide range of amides and peptides containing a Trp moiety. Increasing the sequence length and reaction optimisation made bromination of pentapeptides feasible with good turnovers and a broad sequence scope, while regioselectivity turned out to be sequence dependent. Comparison of X-ray single crystal structures of Thal in complex with d-Trp and a dipeptide revealed a significantly altered binding mode for the peptide. The viability of this bioorthogonal approach was exemplified by halogenation of a cyclic RGD peptide.

Blue fluorescent Zinc(II) complexes bearing schiff base ligand for solution-processed organic light-emitting diodes with CIEy ≤ 0.09

Inspired by the blue fluorescent feature of metal schiff-base complexes, we have been successfully synthesized the blue fluorescent Zn(II) complexes (Zn-1 and Zn-2) bearing pyrazolone based azomethine ligands. The photophysical and electrochemical properties of these complexes have been investigated by several techniques in detail. Both complexes showed the emission in blue region and exhibited a good thermal stability. The single crystal X-ray structure analysis were performed to explicate their coordination adjustment around the Zn(II) metal ion. DFT and TDDFT methods performed to understand the involvement of metal ions and Schiff base ligand in the formation of frontier orbitals. For application in organic light emitting diodes, electroluminescent devices were fabricated by using simple solution-processed fabrication method. The best performance was observed at a low turn-on voltage of 3.5 V with a maximum external quantum efficacy of 3.2% for a deep-blue emission at a CIEy of 0.09.

A crystalline and stable microporous framework based on the dative B←N bonds

<h2>Summary</h2> The concept of making use of dative boron–nitrogen (B←N) bonds for the construction of microporous crystalline organic framework (BNF) materials has been proposed but not fulfilled, and they have not been fully explored for their diverse functions because of the difficulty to stabilize their pore structures under thermal/vacuum activation. In this study, we report the first such stable crystalline framework in which the single-crystal X-ray structures of the as-synthesized BNF-1, activated BNF-1a, and C₂H₂-loaded BNF-1a have been clearly characterized. Here, the 2D framework sheets of BNF-1 were interlocked with one another, generating the stable and crystalline framework with a Brunauer-Emmett-Teller (BET) surface area of 255 m²/g. Also, the material takes up more C₂H₂ than CO₂ molecules, and breakthrough experiments demonstrate its separation performance for C₂H₂/CO₂ mixtures. The molecular recognition mechanism of this BNF-1 for the preferential binding of C₂H₂ molecules over CO₂ has been comprehensively studied by both single-crystal X-ray diffraction and molecular modeling.

Synthesis, Molecular and Supramolecular Structures of Symmetric Dinuclear Cd(II) Azido Complex with bis-Pyrazolyl s-Triazine Pincer Ligand

A new dinuclear Cd(II)-azido complex of 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine (PMT) pincer ligand is synthesized. Its single crystal X-ray structure reveals the dinuclear [Cd(PMT)(Cl)(N3)]2 formula. The triclinic crystal parameters are a = 9.323(4) Å, b = 10.936(5) Å, c = 11.312(6) Å, α = 112.637(10)°, β = 104.547(11)° and γ = 105.133(10)° while V = 944.1(8) Å3. Due to symmetry considerations, the asymmetric unit comprises a half [Cd(PMT)(Cl)(N3)]2 formula. The Cd(II) is hexa-coordinated with one tridentate PMT ligand in a pincer fashion mode in addition to one terminal chloride and two azide ions bridging the two Cd(II) centers in double μ(1,1) bridging mode. Unusually, the Cd-N(s-triazine) bond is not the shortest among the Cd-N interactions with the PMT pincer ligand. The supramolecular structure of the dinuclear [Cd(PMT)(Cl)(N3)]2 formula is controlled by a significant amount of Cl…H (16.4%), N…H (25.3%), H…C (9.8%) and H…H (37.2%) interactions based on Hirshfeld surface analysis. Careful inspection of the shape index map reveals the presence of some weak π-π stacking interactions between the s-triazine and pyrazolyl moieties. The percentage of C…C contacts is 1.9% where the C2…C8 (3.462 Å) is the shortest while the centroid–centroid distance is 3.686 Å. Natural charge analysis describes the charge transferences from the ligand groups to the Cd(II), while and atoms in molecules (AIM) give an indication on the properties of the Cd-N and Cd-Cl bonds.

A Combined Experimental and Theoretical Investigation of Oxidation Catalysis by cis-[VIV(O)(Cl/F)(N4)]+ Species Mimicking the Active Center of Metal-Enzymes.

Reaction of VIVOCl2 with the nonplanar tetradentate N4 bis-quinoline ligands yielded four oxidovanadium(IV) compounds of the general formula cis-[VIV(O)(Cl)(N4)]Cl. Sequential treatment of the two nonmethylated N4 oxidovanadium(IV) compounds with KF and NaClO4 resulted in the isolation of the species with the general formula cis-[VIV(O)(F)(N4)]ClO4. In marked contrast, the methylated N4 oxidovanadium(IV) derivatives are inert toward KF reaction due to steric hindrance, as evidenced by EPR and theoretical calculations. The oxidovanadium(IV) compounds were characterized by single-crystal X-ray structure analysis, cw EPR spectroscopy, and magnetic susceptibility. The crystallographic characterization showed that the vanadium compounds have a highly distorted octahedral coordination environment and the d(VIV-F) = 1.834(1) Å is the shortest to be reported for (oxido)(fluorido)vanadium(IV) compounds. The experimental EPR parameters of the VIVO2+ species deviate from the ones calculated by the empirical additivity relationship and can be attributed to the axial donor atom trans to the oxido group and the distorted VIV coordination environment. The vanadium compounds act as catalysts toward alkane oxidation by aqueous H2O2 with moderate ΤΟΝ up to 293 and product yields of up to 29% (based on alkane); the vanadium(IV) is oxidized to vanadium(V), and the ligands remain bound to the vanadium atom during the catalysis, as determined by 51V and 1H NMR spectroscopies. The cw X-band EPR studies proved that the mechanism of the catalytic reaction is through hydroxyl radicals. The chloride substitution reaction in the cis-[VIV(O)(Cl)(N4)]+ species by fluoride and the mechanism of the alkane oxidation were studied by DFT calculations.

Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate

Nickel–sulfur bonds play key roles in catalysis and biological systems. In most metal complexes, sulfur acts as a bridge joining metal centers, rather than as a terminal sulfide ligand. The addition of phenyl isothiocyanate to Ni(dcpe)(Ph)(SH) afforded the dithiocarbamate complex Ni(dcpe)(κ2-S2C═NPh) with the loss of benzene. The reaction was monitored by UV–visible spectroscopy under pseudo-first-order rate conditions and showed limited dependence on isothiocyanate concentration, suggesting that the reaction proceeds through an intermediate terminal sulfido nickel complex. The values of ΔH⧧ and ΔS⧧ for the reaction were found to be 18.6 ± 1.5 kcal/mol and −17.8 ± 4.7 eu, respectively. Full characterization of Ni(dcpe)(κ2-S2C═NPh), including a single-crystal X-ray structure determination, was achieved.

Crystal structure of a heterotrimetallic 12-metallacrown-4 with 2-propylvalerate anion bridges

The synthesis and single-crystal X-ray structure for tetraaquatetrakis(μ-2-propylvalerato)tetrakis(μ4-salicylhydroximato)dysprosiumtetramanganesesodium dimethylformamide tetrasolvate, [DyMn4Na(C7H4NO3)4(C8H15O2)4(H2O)4]·4C3H7NO or DyNa(2-PV)4[12-MCMnIII Nshi-4](H2O)4·4DMF, 1, where MC is metallacrown, shi3− is salicylhydroximate, 2-PV is 2-propylvalerate, and DMF is N,N-dimethylformamide, is reported. The slightly domed metallamacrocycle contains four ring MnIII ions and four shi3− ligands that generate an [MnIII—N—O] repeat unit that recurs four times. The ring MnIII ions are five-coordinate with a square-pyramidal shape. Furthermore, the metallacrown binds both a DyIII ion and a Na+ ion in the central cavity. The central ions are located on opposite faces of the cavity with the DyIII ion located on the convex side of the MC and the Na+ ion located on the concave side. Each central ion is eight-coordinate although they possess different geometries. The DyIII ion has a square-antiprismatic shape, while the Na+ ion has an extremely distorted biaugmented trigonal–prismatic shape. The four 2-propylvalerate anions help to tether the DyIII to the MC cavity by forming bridges between the DyIII ion and each ring MnIII ion. Moreover, the interstitial DMF molecules are hydrogen bonded to the water molecules that complete the coordination environment of the Na+ ion. The metallacrown framework (excluding the DyIII and Na+ ions), the bridging 2-propylvalerate, and the interstitial DMF molecule experience whole-molecule disorder due to the rotational orientation of the metallamacrocycle. Additionally, the main moiety alkyl chain of the 2-propylvalerate is disordered over two additional orientations, and the main moiety interstitial DMF molecule is disordered over one additional orientation. The main moiety of the metallacrown framework refined to 0.9030 (14), while the minor B-moiety refined to 0.0971 (14). The main moiety alkyl chain of the 2-propylvalerate refined to 0.287 (3): 0.309 (3): 0.307 (3), and the minor B-moiety alkyl chain refined to 0.0971 (14). Lastly, the main moiety interstitial DMF refined to 0.549 (3): 0.354 (3), and the minor B-moiety DMF refined to 0.0971 (14).

Selective Turn-On Fluorescence Sensing of Cyanide Using the Pyridoxal Platform of a Ni(II) Complex

Cyanide is a very toxic pollutant to aquatic life and the environment. Analytical methods for the quantitative assay of cyanide, which are rapid, sensitive (low limit of detection), and cost-effective, are in great demand. Colorimetric and fluorometric methods are ideally suited for this purpose. In this report, we describe a Ni(II) complex containing a pyridoxal platform for the rapid and sensitive fluorometric estimation of cyanide. The square-planar Ni(II) complex, [Ni(L)(N3)]·3H2O, where the ligand LH = 4-[(2-dimethylamino-ethylimino)-methyl]-5-hydroxymtheyl-2-methyl-pyridin-3-ol, a Schiff base formed between pyridoxal and (2-dimethylamino)ethyl amine, was synthesized and characterized by various spectroscopic techniques as well as by single-crystal X-ray structure determination. The complex was found to selectively bind CN- in the presence of other biologically important anions such as F-, Cl-, Br-, I-, OAc-, S2-, NO3 -, PO4 3-, SO4 2-, and H2PO4 - in tris-HCl/NaCl buffer [pH = 7.4], and it can be monitored by fluorescence turn-on or by UV-visible spectroscopy. The binding constant of the complex with CN- was estimated to be 2.046 × 1014 M-2 and the limit of detection (LOD) was 9 nM, the LOD being considerably lower than the maximum permissible level of cyanide ions (1.9 μM) in drinking water, as recognized by the World Health Organization (WHO). The effects of pH and temperature on the sensing are also investigated. The Ni(II) complex is also found to bind to calf-thymus DNA very strongly, and the apparent binding constant (K app) was determined to be 1.33 × 107 M-1 by the fluorescence quenching of the ethidium bromide-DNA adduct by the complex.

Spectroscopic, structural and computational studies of thiophenolato bridged dirhenium(III,III) complexes

Thiophenol (HLH), 4-methylthiophenol (HLMe) and 4-chlorothiophenol (HLCl) react with dirhenium(III,II) complex [Re2(µ-O2CCH3)Cl4(µ-dppm)2] (1) (dppm = Ph2PCH2PPh2) in refluxing dry toluene to afford the diamagnetic Re2 6+ complexes of the type [Re2(μ-LR)2Cl4(μ-dppm)2] (2(LR)) [LR = C6H5S–, p-MeC6H4S– and p-ClC6H4S–]. These are the first examples of thiophenolato bridged dirhenium complexes with a Re2 6+ core containing dppm ligand. The spectral properties of the complexes are reported. In the electrochemical experiment, the type 2(LR) complexes show one quasi-reversible one-electron oxidation and one-electron reduction waves. The identity of 2(LMe) has been established by single-crystal X-ray structure determination (Re–Re distance = 2.6178(5) Å) and is shown to have an edge-shared bi-octahedral structure. DFT analysis shows that the highest occupied molecular orbitals are mainly composed of metal δ-based orbitals whereas the lowest unoccupied molecular orbitals are metal π*-based orbitals and the electronic ground state for the 2(LR) complexes is σ2π2δ*2δ2. Time-dependent DFT (TD-DFT) analysis shows that the sharp peak at 455 nm in the experimental UV-vis spectrum is mainly due to the [Cl(π)]→[Re2(π*)] transition.

Synthesis, Structure, and Optical Properties of a Bis-Macrocycle Derived from a Highly Emissive 1,3,6,8-Tetra(1H-pyrrol-2-yl)pyrene.

A tetra-functionalized pyrene precursor 4b is prepared using the Suzuki-Miyaura coupling of 1,3,6,8-tetrabromopyrene with N-Boc-2-pyrroleboronic acid. 4b displayed a blue emission with a high quantum yield (ϕF = 0.89). 4b is subjected to [3 + 2] Lewis acid-catalyzed condensation with 2,2'-bithiophene-dialcohol 5, affording a planar bis-N2S2 internally linked with pyrene. The single-crystal X-ray structure of bis-N2S2 revealed a planar conformation with all of the pyrrolic nitrogens and thiophenic sulfurs pointing toward the macrocyclic core. Further, the reduction of bis-N2S2 was attempted in the presence of Zn/NH4Cl at room temperature in CHCl3. A sharp color change from pink to brown was observed presumably due to the formation of its reduced congener bis-N2S2-2H. However, the reduced species was found to revert back to its oxidized form over a period of 25 min in CHCl3. Density functional theory (DFT) studies reveal that the two monocyclic halves of bis-N2S2-2H exhibit differences in aromaticity depending on amino and imino pyrroles present inside each individual core. Such a conversion was also monitored by ultraviolet-visible (UV-vis) absorption spectral studies, and the exact composition of bis-N2S2-2H was confirmed by High-resolution/mass spectrometry (HR/MS) analysis. Experimental and theoretical studies reveal a weak aromatic character of bis-N2S2 due to the absence of global conjugation.

Crystal Structures of Half-Sandwich Ru(II) Complexes, [(η6-p-Cymene)(3-chloro-6-(1H-pyrazol-1-yl)pyridazine)Ru(X)]BF4, (X = Cl, Br, I)

Herein, we report the synthesis and single-crystal X-ray structures of three (η6-p-cymene)Ru(II) tetrafluoroborate salts, viz., [(η6-p-cymene)(3-chloro-6-(1H-pyrazol-1-yl)pyridazine)Ru(X)]BF4, (X = Cl, Br, I), Ru1-3. They were prepared by the reactions of [(η6-p-cymene)Ru(μ-X)(X)]2, (X = Cl, Br, I) with two-mole equivalents of 3-chloro-6-(1H-pyrazol-1-yl)pyridazine, under inert conditions at ambient temperatures, and subsequently precipitated by the addition of excess BF4− ions. Orange crystalline precipitates were obtained in good yields, from which the respective single crystals for X-ray diffraction analysis were recrystallized by slow evaporation from their methanolic/diethyl ether solutions. The Ru(II) complexes were characterized by various spectroscopic techniques and chemical methods, which included FTIR, 1H/13C NMR, UV-visible absorption, mass spectrometry, and elemental analysis. The molecular structures were solved by single-crystal X-ray crystal diffraction analysis. The complexes crystallized in the monoclinic crystal system in the P21/c (Ru1-2) and P21/n (Ru3) space groups. Density Functionals Theoretical (DFT) calculations were performed in methanol to gain an understanding of the electronic and structural properties of the complexes. Trends in the data metrics were established, and selected data were compared with the diffraction data. The electrophilicity indices of Ru1-3 follow the order Ru3 &gt; Ru2 &gt; Ru1, and the trend is in line with their anticipated order of reactivity towards nucleophiles.

Structural, DFT calculations and photophysical and photochemical characteristics of 1-((E)-2-phenylethenyl)-2-(4-(2-((E)-2-phenylethenyl) phenoxy) butoxy) benzene (PPPBB)

X-ray single crystal structure and spectroscopic and photophysical parameters of the titled compound were studied. The titled compound shows thermal stability prior to melting at 126.17 °C with Δ H value of 109.991 J g−1. Photophysical parameters include singlet electronic absorption, molar absorption coefficient, oscillator strength, and dipole moment of electronic transition, fluorescence spectra, excited state lifetime, and fluorescence quantum yield for 1-((E)-2-phenylethenyl)-2-(4-(2-((E)-2-phenylethenyl) phenoxy) butoxy) (PPPBB) in different solvents. PPPBB displays a little change in maximum absorption and emission spectra with solvent polarity, indicating a slight change in dipole moment of dye molecules upon excitation. The dipole moments' (Δ μ) difference between the excited and ground states was obtained from the Lippert–Mataga method. Ground and electronic excited states' geometric optimization was performed using density functional theory (DFT) and time-dependent density functional theory (time dependent-DFT), complemented with spectral findings. A good agreement between theoretical data and experimental observations was found. The net photochemical quantum yield (φc) of PPPBB dye was calculated in various solvents.

Structure, optical absorption and NIR-Photoluminescence of ternary Neodymium (III) complexes with fluorinated β-diketone and heterocyclic Lewis bases

Four heteroleptic neodymium complexes, [Nd(fod)3(phen)] (Nd-1), [Nd(fod)3(bpy)] (Nd-2), [Nd(fod)3(im)2] (Nd-3) and [Nd(fod)3(μ-bpp)Nd(fod)3] (Nd-4) (fod is the anion of 6,6,7,7,8,8,8- heptafluoro-2,2-dimethyl-3,5-ocanedione (Hfod), phen is 1,10-phenanthroline, bpy is 2,2′-bipyridine, im is imidazole and bpp is 2,3-bis(2-pyridyl) pyrazine) are synthesized and thoroughly characterized by elemental analysis, TGA, DTA, 1H NMR and infra-red spectroscopy. The complexes Nd-3 and Nd-4 are new; however, the synthesis of Nd-1 and Nd-2 has been reported elsewhere and were resynthesized to investigate their photoluminescence properties. The complexes, retain their identity at higher temperatures and evaporate in the temperature range between 220 and 327-°C without decomposition. The single crystal X-ray structure has been determined for the Nd-1 complex, and ground state geometries of the other three complexes have been predicted using the Sparkle/PM7 model. The optical absorption in different solvents is studied and evaluated in terms of oscillator strength and band shape. The oscillator strength of the hypersensitive 4G5/2,2G7/2 ← 4I9/2 transition is highest in non-coordinating solvents (chloroform and dichloromethane), indicating that the ligand environment around the metal ion is adequately asymmetric. The near IR luminescence, decay curves, and intrinsic quantum yield of these complexes in chloroform are investigated and discussed. It is observed that the replacement of water molecule from the inner coordination sphere of [Nd(fod)3(H2O)] (τ = 1.37µs) by different ancillary ligands markedly enhance the decay time; Nd-2 (2.06 µs) > Nd-4 (1.98 µs) > Nd-1 (1.82 µs) > Nd-3 (1.38 µs) and intrinsic quantum yield (Nd-2 (0.82) > Nd-4 (0.79) > Nd-1 (0.73) > Nd-3 (0.55) of the complexes in chloroform. The scheme energy transfer process is presented, and it has been shown that the ancillary ligands are efficient in enhancing luminescence in the complexes. The CH vibrational quenching of the excited state of Nd3+ can effectively be reduced by using fluorinated ligands in the coordination sphere.

Artificial Water Channels—Progress Innovations and Prospects

Artificial Water Channels—Progress Innovations and Prospects

Ionic Dioxidovanadium(V) Complexes with Schiff-Base Ligands as Potential Insulin-Mimetic Agents—Substituent Effect on Structure and Stability

Four dioxidovanadium(V) complexes with Schiff-base ligands based on 2-hydroxybenzhydrazide with four different substituted salicylaldehydes (5-chlorosalicylaldehyde, 3,5-dichlorosalicylaldehyde, 5-nitrosalicylaldehyde, 3-bromo-5-chlorosalicylaldehyde) were synthesized and described, by using V2O5 and triethylamine. The single crystal X-ray structure measurements as well as elemental analyses and IR spectra confirmed the formulas of the ionic complexes with a protonated triethylamine acting as counterion, HTEA[VO2(L)] (HL = Schiff-base ligand). The kinetic stability of the complexes at pH = 2 and 7 was discussed with respect to the neutral vanadium(V) complexes previously studied as potential insulin-mimetic agents. A correlation between the substituents in an aromatic ring of the Schiff-base ligands with crystal packing, and also with the stability of the compounds, was presented.

A colorimetric and ratiometric fluorescence probe for Zn2+ and Cd2+ with 1,10-phenanthroline derivative

A colorimetric and ratiometric fluorescent probe 2-([1, 1′-biphenyl]-4-yl)-2, 3b,11a,11b-tetrahydro-1H-imidazo[4,5-f][1,10]phenanthroline (probe 1), was designed and synthesized for sensitive and selective detection of Zn2+ and Cd2+ in methanol, test paper and actual water samples. When probe 1 was excited at 350 nm in methanol solution, in the presence of alkali metal ions, alkali-earth metal ions and a variety of transition metal ions, it showed sensitive fluorescence selectivity to Zn2+ and Cd2+. With the addition of Zn2+, the color of the solution changed from purple to green with the naked eye, and with the addition of Cd2+, the color of the solution changed from purple to cyan. The fluorescence intensity of probe 1 showed a good linear relationship with Zn2+ and Cd2+ concentrations, and the detection limits of both Zn2+ and Cd2+ were 0.11 μM. The binding mode of probe 1 and Zn2+ was discussed according to the 1-Zn single X-ray crystal structure. In addition, the results of strip test and real water sample test showed that probe 1 has potential application prospect in environmental ion recognition.

Optimizing the SYBR green related cyanine dye structure to aim for brighter nucleic acid visualization

In recent years, the studies of RNA and its use for the development of RNA based vaccines have increased drastically. Although cyanine dyes are commonly used probes for studying nucleic acids, in a wide range of applications, there is still a growing need for better and brighter dyes. To meet this demand, we have systematically studied the structure of SYBR green-related cyanine dyes to gain a deeper understanding of their interactions with biomolecules especially how they interact with nucleic acids and the structural components which makes them strongly fluorescent. Herein, five new dyes were synthesized, and their photophysical properties were evaluated. Observations of photophysical characteristics were compared to calculations by using density functional theory in its ground state and time-dependent form to model the optical absorption spectra and excited state properties of the selected molecules. Single crystal X-ray crystal structures of five cyanine dyes were determined and the interactions of the cyanine dye-DNA complex were studied by using molecular docking and molecular dynamics calculations. Three molecular structural features were discovered: a) removing the benzene ring from the thiazolium moiety of the dye lowers the fluorescence drastically, and that the quantum yield can be enhanced, therefore increasing the fluorescence, by b) incorporating methanethiol substituent at the quinoline moiety instead of dimethylamine or c) changing the thiazolium moiety to an oxazolium moiety.

Design, synthesis and antitumor efficacy evaluation of a series of novel β-elemene-based macrocycles

β-Elemene is the major constituent of the antitumor drugs elemene extract approved in China. By incorporating macrocyclization strategy into the β-elemene skeleton, we designed a series of novel macrocycles retaining three key carbon–carbon double bonds. Four different methods have been successfully developed for these challenging ring systems. A total of twenty-eight 14- to 24-membered macrocycles were synthesized. Most of these macrocycles exhibited good antitumor activity against several cancer cell lines (PC-3, A549, U87MG, U251 and HCT116), with up to 40 folds improvement of activity comparing to β-elemene. Additionally, X-ray single crystal structures of compounds Ic, Ip, and IIh were successfully solved as the proof of macrocycle formation. The results warrant the further investigation of this novel class macrocycles in pharmacokinetic and pharmacodynamics studies, which will be reported in due course.

Structure-bandgap tunability of metal halide perovskites: Synthesis, spectral, single crystal X-ray structural, BVS, CShM and Hirshfeld surface analysis of piperidinium hexahalostannates(IV)

Metal halide perovskites such as piperidinium hexachlorostannate(IV) and piperidinium hexabromostannate(IV) were prepared along with their ammonium analogues ((1) and (2)) and were analyzed by IR, 1H, 13C NMR, DRS techniques. Single crystal X-ray structures were determined and Bond valence sums (BVS), Continuous Shape Measure (CShM) parameters were deduced from structural data. Broad IR bands were observed for υNH2 vibrations (3388, 3383 cm–1) long with characteristic δNH bending vibrations (1571, 1573 cm–1). TG–DT analysis confirmed the proposed formulae of (1) to (4). Band gaps of the hybrids derived from the DRS study followed the decreasing order: (NH4)2SnCl6 >(C5H10NH2)2SnCl6 >(NH4)2SnBr6 > (C5H10NH2)2SnBr6. Ammonium hybrids (1) & (2) and the piperidinium analogues (3) & (4) are isostructural. Differentiation of Sn-Xaxial/equatorial bonds and distortion of X–Sn–X bond angles observed in (3) and (4) are due to the substitution of ammonium cation by bulky piperidinium cation. The crystal structures are stabilized by intermolecular N–H···X interactions. BVS for (1), (2), (3) and (4) are: 4.12, 4.01, 3.96 and 3.92 respectively, which established the formal oxidation state of tin as quadripositive. CShM for (1), (2), (3) and (4) are: 0.0000, 0.0000, 0.0172 and 0.0103 respectively, indicating octahedral environment of halogen atoms around tin. Shape Index map of (C5H10NH2)2SnBr6 (4) with the least band gap tends to be spherical compared to other compounds.