Cu(II)-Organic Framework for Carboxylative Cyclization of Propargylic Amines with CO.

Effective CO transformations hold essential significance for carbon neutrality and sustainable energy development. Carboxylative cyclization of propargylic amines with CO serves as an atom-economic reaction to afford oxazolidinones, showing broad applications in organic synthesis and pharmaceutical fields. However, most catalysts involved noble metals, exhibited low efficiency, or required large amounts of base.

Metal Hydrogen-Bonded Organic Frameworks as Open Lewis Acid Catalysts for Two Types of CO Transformations.

Efficient and multiple CO utilization into high-value-added chemicals holds significant importance in carbon neutrality and industry production. However, most catalysis systems generally exhibit only one type of CO transformation with the efficiency to be improved. The restricted abundance of active catalytic sites or an inefficient utilization rate of these sites results in the constraint.

A terpyridyl-rhodamine hybrid fluorescent probe for discriminative sensing of Hg (II) and Cu (II) in water and applications for molecular logic gate and cell imaging.

Sensitive and discriminative sensing of more than one analyte with a single fluorescent probe is significant and challenging. Herein a new terpyridyl-rhodamine hybrid, namely TRH, has been rationally designed and prepared with two responsive groups in the molecular structure, which facilitate the discriminative detection of Hg and Cu ions in water with detection limits of 4.9 and 53.

A pyridyl functionalized rhodamine chemodosimeter for selective fluorescent detection of mercury ions and cell imaging.

Rhodamines gain sustained attention owing to their great potential for probe design applications. Herein, the facile preparation of a new pyridyl functionalized rhodamine dye PR is reported, which has stable fluorescence signal in water with maximum emission peak at 594 nm and Stokes shift of 81 nm. Based on dye PR, a new fluorescent probe PRHg has been developed by modifying the spirolactone of PR with hydrazine hydrate so as to produce spirolactam recognizing group for sensing of Hg.

A quinoline-rhodamine hybrid probe for ratiometricly sensing of Hg in water and cell imaging application.

To develop efficient tools for monitoring toxicant Hg in aqueous solution attracts great attention because the abnormal distribution of Hg in environment poses great threat to human health. We here report the preparation of a novel quinoline-rhodamine hybrid fluorescent probe P7RHg for ratiometricly sensing of Hg in water, with a spirolactam-thiosemicarbazide reaction group. Upon treatment by Hg, the ratio of fluorescence intensity (F/F) exhibits nearly 90-fold enhancement, presenting two well-resolved emission peaks (140 nm).

A new zinc-organic framework with 1D channel for constructing a ratiometric Al-selective sensor and four inputs INHIBIT logic gate.

To develop Al fluorescent sensor is significant because the abnormal levels of Al in environment may pose great threat to human body. Herein, a novel metal-organic framework {Zn(Dpada)(Imdba)·HO} (Dpada = 3, 6-di(1H-imidazol-1-yl) pyridazine and Imdba = 2, 2'-iminodibenzoic acid), named Zn-MOF, has been architected with one-dimensional channel under hydrothermal conditions. Zn-MOF exhibits good thermal and solvent stability and can also keep structural integrity over the pH range of 5.

Tetraphenylpyrazine-Based Manganese Metal-Organic Framework as a Multifunctional Sensor for Cu, Cr, MnO, and 2,4,6-Trinitrophenol and the Construction of a Molecular Logical Gate.

A tetraimidazole-decorating tetraphenylpyrazine has been designed and utilized for the fabrication of a novel metal-organic framework (MOF), denoted as {Mn(Tipp)(A)}·2HO (TippMn, where Tipp = 2,3,5,6-tetrakis[4-[(1-imidazol-1-yl)methyl]phenyl]pyrazine and A = deprotonation of 1,4-naphthalenedicarboxylic acid), through hydrothermal synthesis. Structural analysis reveals that TippMn possesses a 2-fold-interpenetrated 4,8-connected three-dimensional (3D) network with an unprecedented {4·6}{4·6} topology. Fluorescent spectral investigations indicate that TippMn shows discriminative fluorescence when treated by Cr and Cu, giving an INHIBIT logical gate performance.

A dual-response fluoran-phenothiazine hybrid fluorescent probe for selective sensing of Fe and ClO and cell imaging application.

Bifunctional fluorescent probes with dual-emission response attract extensive attention. A novel fluorescent probe FP, a hybrid of fluoran and phenothiazine, has been designed and synthesized for selective sensing of Fe and ClO with dual-emission changes, which involes mechanisms of Fe-promoted spirolactone ring opening and ClO-induced oxidation of phenothiazine moiety, respectively. In addition, the detection limits for Fe and ClO were estimated to be 49.

From K[ZnBPO] to K[(ZnAl)PO]: Substitution-Induced Microporous Zincoaluminophosphate with a Congruent-Melting Behavior.

An open-frame aluminophosphate, K[(ZnAl)PO] (KZAPO), was rationally designed by a substitution design strategy and synthesized by a high-temperature molten salt method. Compared with the parent crystal of K[ZnBPO], KZAPO was characterized by similar 4 × 8 × 8 networks, a comparable short-wave ultraviolet transparency and a more regular tetrahedral frame with the mixing of (ZnO) and (AlO) anionic groups, highlighting the multifunctional roles that anionic group mixing played in structural and property modulations. In particular, KZAPO was characterized by a high thermal stability (over 850 °C) and a congruent-melting behavior, being conducive to practical applications.

A Fluoran-Based Cu-Selective Fluorescent Probe and its Application in Cell Imaging.

Based on a fluoran skeleton, we herein reported a new fluorescent probe FLACu for Cu by facile modification of the spirolactone of dye 1 with phenylhydrazine. Taking advantage of the spirolactam moiety, FLACu only delivers a specific "off-on" fluorescence signal output towards Cu when treated with various metal ions, which has been well elucidated as the result of spirolactam ring opening and hydrolysis processes induced by copper ion. Meanwhile, the limit of detection (LOD) for FLACu has been estimated to be 35.

A fluoran-based viscosity probe with high-performance for lysosome-targeted fluorescence imaging.

A new fluorescent probe Lyso-Fl has been facilely prepared by an esterification reaction of spironolactone fluoran dye Rdi with ethanol, which shows viscosity-selective response by fluorescence. The new probe delivers obvious fluorescence signal enhancement when environmental viscosity changes from 1.01 cP (water) to 1256 cP (98% glycerol).

Temperature-induced structural diversity of metal-organic frameworks and their applications in selective sensing of nitrobenzene and electrocatalyzing the oxygen evolution reaction.

Structural diversities are presented in four new Co-MOFs containing 1,5-bi(imidazolyl)anthracene and different dibenzobarrelene skeletons based on dicarboxylic acid, in which MOFs 1-3 exhibit 2D networks in a 4-connected node topology with the point symbol of {4·6}, while MOF 4 forms a 1D chain structure. It is clearly observed that the 2D-1D structural transformation of 2-4 has been realized by temperature modulated hydrothermal synthesis procedures from 120-160 °C, suggesting the key role of temperature for constructing MOFs. In addition, obvious π-π interactions between anthracene rings can be observed in the architectures of 1-3, which may favorably stabilize their 2D supramolecular networks.

A Novel Biscarbazole-Xanthene Hybrid Fluorescent Probe for Selective and Sensitive Detection of Cu and Applications in Bioimaging.

A new biscarbazole-fused xanthene hybrid dye MeBCX has been prepared by CHSOH-promoted condensation of 4-hydroxycarbazole and o-phthalic anhydride, followed by esterification with methanol, which exhibits good cell membrane permeability. Taking advantage of the spiro-controlled xanthene platform of the dye, a Cu-selective fluorescence "off-on" probe BCX-Cu has been successfully prepared with excellent performances in selectivity and sensitivity, and the detection limit is calculated to be 88.7 nM.

Stable Lanthanide-Organic Framework as a Luminescent Probe To Detect Both Histidine and Aspartic Acid in Water.

A three-dimensional metal-organic framework (MOF) {[Eu(L)(HO)]·DMF} (1) (HL = 2'-nitro-3,4',5-biphenyl tricarboxylic acid) was obtained by hydrothermal methods and was characterized in detail. Compound 1 contains [Eu] binuclear units, and [Eu] units are further linked by HL, forming a three-dimensional structure. Stability tests suggest that compound 1 exhibits high solvent, pH, and thermal stability.

Hydrothermal synthesis and structural characterization of metal-organic frameworks based on new tetradentate ligands.

The hydrothermal reaction of two new tetradentate ligands with different metal salts of cadmium nitrate, zinc chloride, cobalt nitrate and deprotonated terephthalic acid (H2tp), isophthalic acid (H2ip), 4,4'-oxybisbenzoic acid (H2obba) in H2O/DMF or H2O/methanol gave three metal-organic frameworks (MOFs): {[Zn2(L1)(tp)(formate)2]·H2O}n (), {[Cd2(L2)(ip)2]·2H2O}n (), {[Co2(L2)(obba)2]}n () (L1 = 1,2-bis {2,6-bis [(1H-imidazol-1-yl) methyl]-4-methylphenoxy} ethane, L2 = 1,3-bis {2,6-bis [(1H-imidazol-1-yl) methyl]-4-methylphenoxy} propane). The structures of the frameworks are established by single-crystal X-ray diffraction. Compound is a three-dimensional (3D) framework with a 2-fold interpenetrated form, which exhibits a 2-nodal (3,4)-connected fsh-3,4-P21/c net with a {8(3)}2{8(5)·10} topology.

1-[3-(Anthracen-9-yl)-5-(pyridin-2-yl)-4,5-dihydro-1H-pyrazol-1-yl]ethanone.

In the title compound, C(24)H(19)N(3)O, the pyrazoline ring adopts an envelope conformation with the C atom linking to the pyridine ring as the flap. The mean plane of the pyrazoline ring makes dihedral angles of 85.54 (4) and 81.

3-[(8-But-oxy-quinolin-2-yl)meth-yl]-1-(pyridin-2-ylmeth-yl)-1H-imidazol-3-ium hexa-fluoridophosphate.

In the cation of the title compound, C(23)H(25)N(4)O(+)·PF(6) (-), the imidazolium ring make dihedral angles of 87.20 (6) and 79.89 (5)° with the pyridine ring and the quinoline system, respectively.

Bis[1-benzyl-3-(4-methyl-phen-yl)imidazol-2-yl-idene]silver(I) hexa-fluorido-phosphate.

The title silver N-heterocyclic carbene compound, [Ag(C(17)H(16)N(2))(2)]PF(6), crystallizes as a mononuclear salt. The two imidazole rings, which are almost coplanar [maximum deviation from the least squares plane of 0.05 (2) Å], are linked by the Ag atom with a C-Ag-C angle of 178.

3,3'-Dimethyl-1,1'-(methyl-enedi-p-phenyl-ene)diimidazolium bis-(hexa-fluoro-phosphate).

The title N-heterocyclic carbene compound, C(21)H(22)N(4) (2+)·2PF(6) (-), crystallizes as an inversion twin. There are two independent N-heterocyclic carbene dications (A and B) and four independent hexa-fluoro-phosphate anions in the asymmetric unit. The cations are L-shaped with the benzene rings being inclined to one another by 88.

Diacetonitrile-(3-{2-[8-(2-bromo-eth-oxy)-9,10-dioxoanthracen-1-yl-oxy]eth-yl}-1-(2-pyridyl-meth-yl)imidazolium)silver(I) bis-(hexa-fluorido-phosphate).

The title compound, [Ag(C(27)H(23)BrN(3)O(4))(CH(3)CN)(2)](PF(6))(2), is a mononuclear salt species in which the silver(I) atom is coordinated by one ligand and two acetonitrile mol-ecules and exhibits a distorted T-shaped coordination. The asymmetric unit contains one independent cation and two independent hexa-fluorido-phosphate anions, one of which is disordered over two positions in a 0.756 (11):0.

N,N'-Bis(4-nitro-phen-yl)biphenyl-2,2'-dicarboxamide.

In the title compound, C(26)H(18)N(4)O(6), the amide units are approximately coplanar with the benzene ring bonded to the N atom [dihedral angles of 10.59 (10) and 24.00 (12)°], but twisted significantly out of the plane of the benzene ring bonded to the carbonyl C atom [dihedral angles of 57.

1-{2-[2-(1H-Benzimidazol-1-yl)eth-oxy]eth-yl}-1H-benzimidazol-3-ium hexa-fluoro-phosphate.

In the title salt, C(18)H(19)N(4)O(+)·PF(6) (-), the dihedral angle between the benzimidazolium and benzimidazole ring systems is 16.24 (2)°. In the cation, a π-π inter-action is observed between the imidazolium ring and the benzene ring of the benzimidazole ring system [centroid-centroid distance = 3.

N-(2-Amino-phen-yl)-2-anilinobenzamide.

In the title compound, C(19)H(17)N(3)O, the planes of the aromatic substituents attached to the benzamide moiety are almost perpendicular to one another, making a dihedral angle of 88.16 (7)°. The observed conformation of the mol-ecule is produced by an intra-molecular N-H⋯O hydrogen bond.

2-Anilino-N-methyl-N-phenyl-benzamide.

The title compound, C(20)H(18)N(2)O, is composed of three aromatic rings, the dihedral angles between the phenyl and benzamide rings, and between the benzamide and aniline rings being 59.86 (9) and 46.57 (10)°, respectively.

N-Phenyl-anthranilic anhydride.

The complete mol-ecule of the title compound, C(26)H(20)N(2)O(3), is generated by crystallographic twofold symmetry, with the central O atom lying on the rotation axis. The conformation is stabilized by an intra-molecular N-H⋯O hydrogen bond. The dihedral angle between the inner and outer aromatic ring planes is 61.