Metal Hydrogen-Bonded Organic Frameworks as Open Lewis Acid Catalysts for Two Types of CO2 Transformations.

Efficient and multiple CO2 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 CO2 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. Consequently, we designed and constructed two metal hydrogen-bonded organic frameworks (M-HOFs) {[M3(L3-)2(H2O)10]·2H2O}n (M = Co (1), Ni (2); L = 1-(4-carboxyphenyl)-1H-pyrazole-3,5-dicarboxylic acid) in this research. 1 and 2 are well-characterized, and both show excellent stability. The networks connected by multiple hydrogen bonds enhance the structural flexibility and create accessible Lewis acidic sites, promoting interactions between the substrates and catalytic centers. This enhancement facilitates efficient catalysis for two types of CO2 transformations, encompassing both cycloaddition reactions with epoxides and aziridines to afford cyclic carbonates and oxazolidinones. The catalytic activities (TON/TOF) are superior compared with those of most other catalysts. These heterogeneous catalysts still exhibited high performance after being reused several times. Mechanistic studies indicated intense interactions between the metal sites and substrates, demonstrating the reason for efficient catalysis. This marks the first instance on M-HOFs efficiently catalyzing two types of CO2 conversions, finding important significance for catalyst design and CO2 utilization.

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 Hg2+ and Cu2+ ions in water with detection limits of 4.9 and 53.3 nM by ratiometric fluorescence change (F595/F485) and fluorescence quenching, respectively. Investigations show that the selectivity to Hg2+ ions can be attributed to Hg2+-promoted spirolactam ring opening and further hydrolysis, followed by a through-bond energy transfer (TBET) process. The selective fluorescence quenching to Cu2+ ions probably can be ascribed to the binding Cu2+ to terpyridyl that triggers a ligand-to-metal charge transfer (LMCT) process, which can also efficiently inhibit the TBET process induced by Hg2+ ions and promotes the discriminative sensing of Cu (II) and Hg (II). In addition, the fluorescent responses to Hg2+ and Cu2+ ions cover a wide pH range. Moreover, a combinatorial logic gate with the functions of NOR and INHIBIT has been fabricated by using Hg2+ and Cu2+ ions as chemical input signals, and fluorescence at 485 and 595 nm as output signals. Besides, TRH also exhibits sensitive and discriminative sensing ability to Hg2+ and Cu2+ ions by the fluorescence of rhodamine fluorophore. Significantly, based on the fluorescence signal output of rhodamine moiety, TRH can be used as a tracer for the discriminative sensing of Hg2+ and Cu2+ ions by using living cells.

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 Hg2+. PRHg exhibits high selectivity and sensitivity towards Hg2+ in water/ethanol (v/v = 4/1, pH = 7.0) by a specific Hg2+-binding promoted spirolactam ring opening and hydrolyzing process. And, the detection limit for Hg2+ is evaluated to be 8.5 nM. Besides, the probe can respond to Hg2+ within 40 min and over a wide pH range from 4.0 to 10.0. Moreover, PRHg (40 µM) performs low cytotoxicity to HeLa cells (over 91.0 % cell survival rate), which allows the probe to be employed for tracing intracellular Hg2+ by fluorescence imaging.

A quinoline-rhodamine hybrid probe for ratiometricly sensing of Hg2+ in water and cell imaging application.

To develop efficient tools for monitoring toxicant Hg2+ in aqueous solution attracts great attention because the abnormal distribution of Hg2+ 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 Hg2+ in water, with a spirolactam-thiosemicarbazide reaction group. Upon treatment by Hg2+, the ratio of fluorescence intensity (F600/F460) exhibits nearly 90-fold enhancement, presenting two well-resolved emission peaks (140 nm). Meanwhile, the specific Hg2+-induced desulfurization provides probe P7RHg an excellent selectivity to Hg2+, with a detection limit of 8.6 nM. Moreover, the low cytotoxicity allows P7RHg to be employed for tracing Hg2+ in living cells by confocal fluorescence imaging.

A new zinc-organic framework with 1D channel for constructing a ratiometric Al3+-selective sensor and four inputs INHIBIT logic gate.

To develop Al3+ fluorescent sensor is significant because the abnormal levels of Al3+ in environment may pose great threat to human body. Herein, a novel metal-organic framework {Zn(Dpada)(Imdba)·H2O}n (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 5.0 - 9.0. Fluorescent experiments show that Zn-MOF has high selectivity and sensitivity towards Al3+ via ratiometric fluorescence signal changes (F470 nm/F390 nm) and the detection limit is evaluated to be 0.69 µM. In addition, Zn-MOF performs good recyclability in sensing of Al3+ with at least 5 cycles. Besides, an INHIBIT logic gate has been constructed with chemical ions (Al3+, Cr3+, Fe3+ and Hg2+) as input signals and emission ratio (F470 nm/F390 nm) as output signal. Significantly, Zn-MOF can be applied to tracing Al3+ using real water samples, presenting great potential in water quality monitoring application.

Tetraphenylpyrazine-Based Manganese Metal-Organic Framework as a Multifunctional Sensor for Cu2+, Cr3+, MnO4-, 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)2}n·2H2O (TippMn, where Tipp = 2,3,5,6-tetrakis[4-[(1H-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 {416·612}{44·62} topology. Fluorescent spectral investigations indicate that TippMn shows discriminative fluorescence when treated by Cr3+ and Cu2+, giving an INHIBIT logical gate performance. Meanwhile, TippMn can be further used as a sensor for MnO4- and 2,4,6-trinitrophenol (TNP) by fluorescence quenching. Notably, the sensing processes toward Cu2+, Cr3+, MnO4-, and TNP are labeled with high selectivity and sensitivity, quick response, and good recyclability. It is anticipated that this MOF-based versatile sensor could shed light on the exploration of MOFs for fluorescent sensors, optical switches, etc.

A dual-response fluoran-phenothiazine hybrid fluorescent probe for selective sensing of Fe3+ 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 Fe3+ and ClO- with dual-emission changes, which involes mechanisms of Fe3+-promoted spirolactone ring opening and ClO--induced oxidation of phenothiazine moiety, respectively. In addition, the detection limits for Fe3+ and ClO- were estimated to be 49.1 and 35.9 nM, respectively. Significantly, FP can be employed as an tracer for the detection of Fe3+ ions within living HeLa cells by fluorescence imaging.

From K[ZnBP2O8] to K[(Zn0.5Al0.5)2P2O8]: Substitution-Induced Microporous Zincoaluminophosphate with a Congruent-Melting Behavior.

An open-frame aluminophosphate, K[(Zn0.5Al0.5)2P2O8] (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[ZnBP2O8], 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 (ZnO4)6- and (AlO4)5- 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 Cu2+-Selective Fluorescent Probe and its Application in Cell Imaging.

Based on a fluoran skeleton, we herein reported a new fluorescent probe FLACu for Cu2+ 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 Cu2+ 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 35.4 nM and a pH range of 5.0-9.0 is evaluated to be suitable for Cu2+ detection. Significantly, FLACu shows low cell cytotoxicity and can be further ultilzied in the detection of exogenous Cu2+ in the living Hela cells.

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). And, both the emission intensity (575 nm) and fluorescence lifetime of Lyso-Fl exhibit individually good linear relationships with the solution viscosity. Besides, Lyso-Fl gives a selective response to viscosity among various biological species and exhibits pH-independent (1-10) fluorescent signals towards viscosity. More importantly, Lyso-Fl shows low cytotoxicity and can be utilized for monitoring of dexamethasone-stimulated viscosity enhancement by cell imaging with excellent lysosome-targeted performance, promoting it a promising fluorescent probe for lysosomal viscosity detection.

A Novel Biscarbazole-Xanthene Hybrid Fluorescent Probe for Selective and Sensitive Detection of Cu2+ and Applications in Bioimaging.

A new biscarbazole-fused xanthene hybrid dye MeBCX has been prepared by CH3SO3H-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 Cu2+-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. The sensing mechanism is confirmed to involve a specific cascade reactions of Cu2+-induced spirolactam ring-opening and hydrolysis. In addition, living L929 cell imaging demonstrates the probe has living cell membrane permeability and shows great potential for tracing intracellular Cu2+ through fluorescence imaging technology.

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)(H2O)2]·DMF} n (1) (H3L = 2'-nitro-3,4',5-biphenyl tricarboxylic acid) was obtained by hydrothermal methods and was characterized in detail. Compound 1 contains [Eu2] binuclear units, and [Eu2] units are further linked by H3L, forming a three-dimensional structure. Stability tests suggest that compound 1 exhibits high solvent, pH, and thermal stability. Besides, we also explored the influence of pH values in the luminescence emission of 1 which shows that pH has a negligible effect on the luminescence intensity with the range of pH = 3-11. Importantly, luminescent investigations reveal that 1 can selectively detect aspartic acid or histidine among 14 amino acids with good regenerability in water. Meanwhile, the concentration of aspartic acid can be quantitatively determined. We also discuss the mechanism of luminescence quenching and enhancement in detail. Importantly, this Eu-MOF provides a MOF-based luminescence sensor to detect two amino acids for the first time.

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 sql topology with the point symbol of {44·62}, 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. More importantly, fluorescence behaviors of 1-4 have been investigated in water among various nitro-aromatic compounds (NACs) and the results show that all samples exhibit high selectivity and fine sensitivity to nitrobenzene (NB) with fluorescence quenching, which is confirmed to be the result of electron transfer from the excited state of ligands to that of NB by density functional theory. Furthermore, MOFs 1-4 have been directly employed as electrocatalysts for the oxygen evolution reaction (OER), in which MOF 4 gives the best activity towards the OER among all as-synthesized samples with an overpotential of 398 mV at a current density of 10 mA cm-2 and a low Tafel slope of 59 mV dec-1.

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. Compound has a 2-nodal (4,8)-connected 3D framework where the dinuclear cadmium cluster secondary building units (SBUs) assemble with isophthalate and ligand L2 to construct a rare topological type sqc22 net with a {3(2)·5(4)}{3(4)·4(4)·5(10)·6(10)} topology. Whereas, Compound can be extended to a 2D interlocked (4,4)-connected 4,4 L28 net with the point symbol {4·6(4)·8}2{4(2)·6(4)}. L1 and L2 are tetradentate ligands with diverse linkers and display different coordination modes. In addition, the thermal stability and photochemical properties of the frameworks are also investigated.

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. In the crystal, C-H⋯F and C-H⋯N hydrogen bonds are observed.

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 81.66 (3)° with the pyridine ring and the anthracene ring system, respectively. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds. In addition, weak π-π inter-actions [centroid-centroid distances = 3.695 (3)-3.850 (7) Å] are observed.

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 178.60 (9)°. In the crystal, C-H⋯F hydrogen bonds, weak π-π inter-actions [centroid-centroid distances = 3.921 (1) and 3.813 (3) Å] and C-H⋯π inter-actions lead to a supermolecular structure.

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 = 3.5713 (11) Å]. The PF(6) (-) ion is disordered over two sites, with occupancies of 0.895 (2) and 0.105 (2). In the crystal structure, pairs of N-H⋯N hydrogen bonds link the cations, forming centrosymmetric dimers. The dimers are linked via π-π inter-actions [centroid-centroid distance = 3.5606 (11) Å]. In addition, C-H⋯F hydrogen bonds are observed.

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 57.82 (9) and 58.05 (9)°]. The dihedral angle between the two rings of the biphenyl unit is 77.66 (4)°. Intra-molecular N-H⋯O hydrogen bonds and weak C-H⋯O inter-actions occur. The crystal structure is stabilized by inter-molecular N-H⋯O hydrogen bonds and C-H⋯O contacts.

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):0.244 (11) ratio. Weak π-π inter-actions between the anthraquinone ring systems [centroid-centroid distance = 3.676 (3) Å], inter-molecular Ag-π inter-actions [Cg⋯Ag = 3.405 Å] and C-H⋯π inter-actions between pairs of adjacent mol-ecules are observed.