Host-Guest Cocrystallization of Phenanthrene[2]arene Macrocycles Facilitating Structure Determination of Liquid Organic Molecules.

Single-crystal X-ray diffraction analysis has emerged as the most reliable method for determining the structures of organic molecules. However, numerous analytes, such as liquid organic molecules, pose challenges in crystallization, making their structures directly elusive via X-ray crystallography methods. Herein, we introduced the rapid cocrystallization of a macrocycle named phenanthrene[2]arene (PTA, host) with 15 liquid organic molecules (guests). The guest liquid organic molecules were successively cocrystallized with the aid of the PTA host. Moreover, the chemical structures of the liquid organic molecules could be determined through single-crystal X-ray diffraction analysis. PTA exhibited high adaptivity and was capable of encapsulating liquid organic molecules without forming covalent bonds or strong directional interactions. The results revealed that the adaptive crystals of PTA exhibited excellent cocrystallization capacity. Weak noncovalent interactions between the host and guest molecules were crucial for organizing the guests in an ordered pattern.

Synthesis, Structures, and Magnetism of Four One-Dimensional Complexes Using [Ni(CN)4]2- and Macrocyclic Metal Complexes.

Four one-dimensional complexes, denoted as [NiL1][Ni(CN)4] (1), [CuL1][Ni(CN)4] (2), [NiL2][Ni(CN)4]·2H2O (3), and [CuL2][Ni(CN)4]·2H2O (4) (L1 = 1,8-dimethyl-1,3,6,8,10,13-hexaaza-cyclotetradecane; L2 = 1,8-dipropyl-1,3,6,8,10,13-hexaazacyclotetradecane) were synthesized by reacting nickel/copper macrocyclic complexes with K2[Ni(CN)4]. Subsequently, the synthesized complexes were characterized using elemental analysis, infrared spectroscopy analysis, thermogravimetric analysis, and X-ray powder diffraction. Single-crystal structure analysis revealed that the Ni(II)/Cu(II) atoms were coordinated by two nitrogen atoms from [Ni(CN)4]2- with four nitrogen atoms from a macrocyclic ligand, forming a six-coordinated octahedral coordination geometry. Nickel/copper macrocyclic complexes were bridged by [Ni(CN)4]2- to construct one-dimensional chain structures in 1-4. The characterization results showed that the four complexes obeyed the Curie-Weiss law with a weak antiferromagnetic exchange coupling.

Pyromellitic Diimide-Extended Pillar[6]arene: Synthesis, Structure, and Its Complexation with Polycyclic Aromatic Hydrocarbons.

A novel pyromellitic diimide-extended pillar[6]arene was synthesized in two steps with moderate yield for the first time. It showed a symmetrical stretched hexagon structure and could form 1:2 complexes with polycyclic aromatic hydrocarbons in solution. Interestingly, a linear supramolecular array between complex 1@G42 and pyrene through π···π stacking interactions was also observed in the solid state.

Selective difunctionalization of electron-deficient alkynes: access to (E)-2-iodo-3-(methylthio)acrylate.

A convenient and efficient approach to (E)-2-iodo-3-(methylthio)acrylate has been developed through direct iodothiomethylation of alkynes with aqueous HI and DMSO under mild conditions. This novel protocol has demonstrated a unique difunctionalization of electron-deficient alkynes with a broad substrate scope and excellent functional-group tolerance. Preliminary mechanistic studies indicated that prior diiodination of alkynes, followed by nucleophilic substitution with in situ generated DMS led to the formation of (E)-2-iodo-3-(methylthio)acrylate.

Monopeptide-Based Powder Gelators for Instant Phase-Selective Gelation of Aprotic Aromatics and for Toxic Dye Removal.

Through a combinatorial screening of 35 possible phase-selective monopeptide-based organogelators readily made at low cost, we identified five of them with high gelling ability toward aprotic aromatic solvents in the powder form. The best of them (Fmoc-V-6) is able to instantly and phase-selectively gel benzene, toluene, and xylenes in the presence of water at room temperature at a gelator loading of 6% w/v. This enables the gelled aromatics to be separated by filtration and both aromatics and the gelling material to be recycled by distillation. We also identified Fmoc-I-16 as the best gelator for benzyl alcohol, and the corresponding organogel efficiently removes toxic dye molecules by 82-99% from their highly concentrated aqueous solutions. These efficient removals of toxic organic solvents and dyes from water suggest their promising applications in remediating contaminated water resources.

Ligand-Free, Quinoline N-Assisted Copper-Catalyzed Nitrene Transfer Reaction To Synthesize 8-Quinolylsulfimides.

An efficient copper-catalyzed, quinolyl N-directed nitrene transfer reaction to 8-quinolylsulfides was described. A variety of 8-quinolylsulfimides with different functional groups were synthesized in moderate to high yields. The obtained 8-quinolylsulfimides were proved to be promising novel type of bidentate ligands in Pd(II)-catalyzed allylic alkylation.

RuHCl(CO)(PPh3)3-Catalyzed Direct Amidation of Arene C-H Bond with Azides.

We first report the direct ortho C-H amidation of arenes with azides by using a novel and inexpensive RuHCl(CO)(PPh3)3 catalyst. The reaction proceeds efficiently in high yield over a broad range of substrates without requirement of any additional silver salt or additive.

Regioselectivity-Tunable Self-1,3-Dipolar [3+3] Cyclizations of Azomethine Ylides To Assemble Dispirooxindole-piperazines.

A series of novel 2,3- or 2,5-dispirooxindole-piperazine ring systems were efficiently constructed through the acid-promoted self-1,3-dipolar [3+3] cyclizations of azomethine ylides derived from isatin with various primary or cyclic secondary amines. Interestingly, the regioselectivity of this self-[3+3] cyclization could be effectively tuned by varying the structural features of substrates. The unprecedented 2,5-dispirooxindole-piperazine skeleton was achieved in good diastereoselectivity by employing 1,2,3,4-tetrahydroisoquinoline, while using pyrrolidine or glycine methyl ester furnished the 2,3-dispirooxindole-piperazine scaffold in excellent diastereoselectivity (only a single isomer formed).

Functional copper complexes with benzofurans tridentate ligand: Synthesis, crystal structure, DNA binding and anticancer studies.

Metal complexes, particularly copper(II) complexes, are often used as anticancer drugs due to their ability to generate reactive oxygen species (ROS) in cells. Four copper(II) complexes have been designed based on ligands for triplet pyridine derivatives (complexes 1-4), and their structures have been determined using X-ray single crystal analysis. The interactions of these complexes with calf thymus DNA (CT-DNA) have been investigated using various techniques, including UV-vis absorption, viscosity measurements, and circular dichroism spectroscopy. The results indicate that complexes 1-4 strongly interact with DNA through partial intercalations. Further investigation using agarose gel electrophoresis shows that all four complexes can cleave pBR322 DNA in the presence of ascorbic acid as a reducing agent, and the DNA cleavage mechanism is through the generation of singlet oxygen (1O2). In vitro anticancer activities of these complexes have been evaluated using A549, MDA-MB-231, HeLa, and HepG2 cells. The calculated IC50 values indicate significant efficacy against cancer cells. Additionally, AO/EB staining assays reveal that these complexes induce cell apoptosis in HeLa cell line.

catena-Poly[[[(5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane-κ(4)N)nickel(II)]-µ-oxido-[dioxidotungstate(VI)]-µ-oxido] tetra-hydrate].

In the title compound, {[NiWO(4)(C(16)H(36)N(4))]·4H(2)O}(n), the Ni(II) ion lies on an inversion center and is octahedrally coordinated by four N atoms of the tetradentate macrocyclic 5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane (L) ligand in the equatorial plane and two O atoms of [WO(4)](2-) anions in axial positions. Each [WO(4)](2-) anion bridges two adjacent [NiL](2+) cations, forming a chain along [001]. The chains are further connected via N-H⋯O, O-H⋯O and C-H⋯O hydrogen-bonding inter-actions, generating a three-dimensional structure.

Structure and absolute configuration of liquid molecules based on adamantane derivative cocrystallization.

Liquid molecules are difficult to crystallize, and their structures and absolute configurations cannot be directly determined by X-ray crystallography. We herein report the rapid cocrystallization of tetraaryladamantanes with liquid molecules. The structure of the liquid small molecules can be obtained by determining the crystal structure of the cocrystallized compound. The absolute configuration of chiral molecules can also be assigned, which cannot be accomplished by other methods such as nuclear magnetic resonance. In this paper, liquid compounds such as phenylethanol and phenylpropanol derivatives were selected. 1,3,5,7-Tetrakis(2,4-diethoxyphenyl)adamantane (TEO) powder was heated and dissolved in liquid molecules and allowed to stand overnight to undergo cocrystallization. The results show that the single-crystal structures and the absolute configurations of 16 liquid molecules were determined by cocrystallization, and the homochiral natures of chiral compounds were confirmed by solid circular dichroism spectral measurements.

Di-µ-acetato-1:2κO:O';2:3κO:O,O'-bis-(5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)-1κN,3κN-bis-(perchlorato-2κO,O')-2-sodium-1,3-dizinc perchlorate.

In the title salt, [NaZn(2)(CH(3)COO)(2)(ClO(4))(2)(C(16)H(36)N(4))(2)]ClO(4), the macrocyclic ligand binds to the Zn(2+) cations through their four amino N atoms; the Zn(2+) cations are also each covalently bonded to an acetate ion. For one zinc atom, the acetate group is monodentate, and the geometry is a distorted ZnN(4)O trigonal bipyramid; for the other, the acetate group is anisobidentate and the geometry is a distorted ZnN(4)O(2) octa-hedron. The two macrocycle-zinc acetate units are bridged through a diperchloratosodium unit. In the crystal, the complex cations and uncoordinated perchlorate anions are linked by N-H⋯O hydrogen bonds.

(2-Amino-benzoato-κO,O')(rac-5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane-κN,N',N'',N''')nickel(II) perchlorate monohydrate.

In the title salt, [Ni(C(7)H(6)NO(2))(C(16)H(36)N(4))]ClO(4)·H(2)O, the Ni(II) cation is O,O'-chelated by the benzoate anion and N,N',N'',N'''-chelated by the macrocycle ligand, confering a distorted octa-hedral geometry on the metal atom. The complex cations, perchlorate anions and uncoordinated water mol-ecules are linked by N-H⋯O and O-H⋯O hydrogen bonds into a three-dimensional network. The perchlorate ion is disordered over two positions in a 0.554 (8):0.446 (8) ratio.

(2-Carb-oxy-acetato-κO,O)(rac-5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane-κN,N',N'',N''')nickel(II) perchlorate acetonitrile solvate.

In the crystal structure of the title salt, [Ni(C(3)H(3)O(4))(C(16)H(36)N(4))]ClO(4)·CH(3)CN, the macrocycle folds around the Ni(II) atom, which is also chelated by the carboxyl-ate monoanion. The geometry is a distorted NiN(4)O(2) octa-hedron. The formula units are connected by N-H⋯O hydrogen bonds into centrosymmetric dimers. Further N-H⋯O and O-H⋯O hydrogen bonds link the complex mol-ecules and the perchlorate ions.

[4-Carboxy-imidazole-5-carboxyl-ato(2-)-κN,O](5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-decane-κN,N',N'',N''')nickel(II) monohydrate.

The 4-carboxy-imidazole-5-carboxyl-ate(2-) dianion in the title compound, [Ni(C(5)H(2)N(2)O(4))(C(16)H(36)N(4))]·H(2)O, N,O'-chelates to the Ni(II) atom, which shows an octa-hedral coordination. The macrocycle folds itself around the metal atom and binds to it through four secondary nitrogen atoms; adjacent molecules are linked by N-H⋯O hydrogen bonds into a linear chain. The water molecule is disordered over two positions.

cis-[(7R,14R)-5,5,7,12,12,14-Hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-decane-κN](oxalato-κO,O')nickel(II) oxalic acid solvate.

Both mol-ecules of the title compound, [Ni(C(2)O(4))(C(16)H(36)N(4))]·C(2)H(2)O(4), are located on a crystallographic twofold rotation axis. The Ni(II) atom shows a distorted octa-hedral geometry. The crystal packing is stabilized by N-H⋯O and O-H⋯O hydrogen bonds.

(2-Carboxy-benzoato-κO,O)(5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-decane-κN)nickel(II) perchlorate monohydrate.

The title compound, [Ni(C(8)H(5)O(4))(C(16)H(36)N(4))]ClO(4)·H(2)O, has the Ni(II) atom in a distorted octa-hedral geometry, surrounded by coordination by four N atoms of the 5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-decane ligand in a folded configuration, and two carboxyl-ate O atoms of the 2-carboxy-benzoate ligand in cis positions. The complex cation, the disordered perchlorate anion [occupancies 0.639 (8):0.361 (8)] and uncoordinated water mol-ecules engage in N-H⋯O and O-H⋯O hydrogen bonding, forming a layer structure parallel to (010).

Bis(5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-decane-κN)(µ-l-mal-ato-κO,O:O,O)dinickel(II) bis(perchlorate) monohydrate.

In the crystal structure of the title dinuclear compound, [Ni(2)(C(4)H(4)O(5))(C(16)H(36)N(4))(2)](ClO(4))(2)·H(2)O, the bridg-ing di-car-box-yl-ate dianion O,O'-chelates to two Ni atoms, both of which are also chelated by the N-macrocylic ligand. The Ni atoms exhibit a distorted octa-hedral coordination. N-H⋯O and O-H⋯O hydrogen bonds link the cations and the uncoordinated water mol-ecules into a layer structure; the perchlorate anions occupy the space between adjacent layers, and are only weakly linked to the layers. One of the perchlorate anions is disordered over two sets of sites in a 3:2 ratio.

(Benzoato-κO,O')(5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-azacyclo-tetra-decane-κN,N',N'',N''')nickel(II) perchlorate monohydrate.

The Ni atom in the title salt, [Ni(C(7)H(5)O(2))(C(16)H(36)N(4))]ClO(4)·H(2)O, is in a six-coordinate octa-hedral geometry. The metal atom is chelated by the carboxyl-ate group, and the macrocyclic ligand adopts a folded configuration. The cation, anion and water mol-ecules engage in hydrogen bonding to form a layer structure.

catena-Poly[[bis-(µ(2)-4-amino-benzene-sulfonato-κO:O)disilver]-bis-(µ(2)-4,4'-bipyridine-κN:N')].

In the title compound, [Ag(2)(C(6)H(6)NO(3)S)(2)(C(10)H(8)N(2))(2)](n), the Ag(I) atom is four-coordinated by two N atoms from two symmetry-related 4,4'-bipyridine (bipy) and two O atoms from two independent 4-amino-benzene-sulfonate (ABS) ligands. The two inter-chain Ag(I) atoms are bridged by two independent ABS ligands through weak Ag-O bonds and Ag⋯Ag attractions, forming a ladder-like chain coordination polymer [Ag(2)(ABS)(2)(bipy)(2)](n) parallel to [001], which is further linked to generate a two-dimensional structure via N-H⋯O hydrogen-bonding inter-actions.