Cd-MOF and Its Ln3+-Post Modification Products: Regulation of Luminescence Properties and Improved Detection of Uric Acid, Quinine, and Quinidine.

One 3D Cd-MOF, namely, {[(HDMA)2][Cd3(L)2]·5H2O·2DMF}n (LCU-124, LCU indicates Liaocheng University), was synthesized from an ether-containing ligand 1,3-bis(3,5-dicarboxylphenoxy)benzene (H4L). Its Ln3+-postmodified samples, Eu3+@LCU-124 and Tb3+@LCU-124, were obtained through cation exchange of dimethylamine cation (HDMA) with Eu3+ and Tb3+. The successful entry of rare earth into LCU-124 by cation exchange modification was verified by IR, XRD, XPS, EDS mapping, and luminescence spectra. The proportion of Eu3+/Tb3+ was adjusted during the modification process, leading to fluorescent materials with different emissions. Luminescence measurements indicated that these complexes exhibited interesting multiresponsive sensing activities toward biomarkers urine acid (UA), quinine (QN), and quinidine (QND). First, LCU-124 has a pronounced quenching effect toward UA with the detection limit of 31.01 µM. After modification, the visualization of the detection was improved significantly and the detection limit of Eu3+@LCU-124 was reduced to 0.868 µM. Second, when QN and QND were present in the suspensions of Eu3+@LCU-124 and Tb3+@LCU-124, strong blue light emission peaks occurred, while the characteristic emission of Eu3+/Tb3+ decreased, forming ratiometric fluorescent sensors with the detection limit in the range of 0.199-9.49 µM. The fluorescent probes have high selectivity, excellent sensitivity recycling, and fast response time (less than 1 min). Besides, a simple logic gate circuit and a range of luminescent mixed matrix membranes were designed to provide simple and fast detection of above biomarkers. Our work indicated that modification of Eu3+/Tb3+ could improve the detection ability significantly.

Synthesis of π-Conjugated Chiral Organoborane Macrocycles with Blue to Near-Infrared Emissions and the Diradical Character of Cations.

Highly emissive π-conjugated macrocycles with tunable circularly polarized luminescence (CPL) have sparked theoretical and synthetic interests in recent years. Herein, we report a synthetic approach to obtain new chiral organoborane macrocycles (CMC1, CMC2, and CMC3) that are built on the structurally chiral [5]helicenes and highly luminescent triarylborane/amine moieties embedded into the cyclic systems. These rarely accessible B/N-doped main-group chiral macrocycles show a unique topology dependence of the optoelectronic and chiroptical properties. CMC1 and CMC2 show a higher luminescence dissymmetry factor (glum) together with an enhanced CPL brightness (BCPL) as compared with CMC3. Electronic effects were also tuned and resulted in bathochromic shifts of their emission and CPL responses from blue for CMC1 to the near-infrared (NIR) region for CMC3. Furthermore, chemical oxidations of the N donor sites in CMC1 gave rise to a highly stable radical cation (CMC1·+SbF6-) and diradical dication species (CMC12·2+2SbF6-) that serve as a rare example of a positively charged open-shell chiral macrocycle.

Two Co-Based Metal-Organic Framework Isomers with Similar Metal-Carboxylate Sheets: Turn-On Ratiometric Luminescence Sensing Activities toward Biomarker N-Acetylneuraminic Acid and Discrimination of Ga3+ and In3.

Two supramolecular Co-MOF isomers, namely, {[Co(L)0.5(m-bimb)]·3H2O}n (LCU-115) and {[Co(L)0.5(p-bimb)]·3H2O}n (LCU-116), were synthesized from an amide-containing carboxylic acid N,N″-(3,5-dicarboxylphenyl)benzene-1,4-dicarboxamide (H4L) and two flexible positional isostructural N-containing ligands m-bimb and p-bimb (m-bimb = 1,3-bis((1H-imidazol-1-yl)methyl)benzene; p-bimb = 1,4-bis((1H-imidazol-1-yl)methyl)benzene). The carboxylate ligands connect Co(II) centers to form 2D metal-carboxylate sheets, which are extended further by m-bimb and p-bimb to form a 2D bilayer with parallel stacking (LCU-115) and a 3D framework (LCU-116), respectively. Luminescence measurements indicated that these two complexes exhibited interesting multiresponsive sensing activities toward pH, biomarker N-acetylneuraminic acid, and trivalent cations Ga3+/In3+. They show highly sensitive turn-on fluorescence responses in the acidic range and can also be regarded as on-off-on vapoluminescent sensors to typical acidic and basic gases HCl and Et3N. It is worth noting that these complexes have excellent turn-on ratiometric fluorescence sensing ability for N-acetylneuraminic acid (NANA) with detection limits as low as 7.39 and 8.06 µM, respectively. Furthermore, they were successfully applied for the detection of NANA in simulated urine and serum samples with satisfactory results. For ion detection, LCU-116 could detect both Ga3+ and In3+, while LCU-115 could distinguish Ga3+ from In3+ with the latter showing luminescence quenching. The sensing mechanism was investigated in detail by XRD, UV-vis, EDS, XPS, SEM, and TEM. The results of interday and intraday precision studies gave low RSD values in the range of 1.19-3.53%, ascertaining the reproducibility of these sensors. The recoveries for the sensing analytes in simulated urine/serum or real water are satisfactory from 96.7 to 103.3% (toward NANA) and 96.6 to 115.0% (toward Ga3+ and In3+), indicating that these two complexes also possess acceptable reliability for monitoring in real samples. The results indicated that the supramolecular isomers LCU-115 and LCU-116 are promising material candidates for application in biological and environmental monitoring.

Enhancing Proton Conductivity of Nafion Membrane by Incorporating Porous Tb-Metal-Organic Framework Modified with Nitro Groups.

A rigid carboxylate ligand with a nitro functional group was selected to coordinate with Tb(III) cation, and Tb-MOF ({[Tb4(L)4(OH)4(H2O)3]·8H2O}n, H2L = 2-nitroterephthalic acid) with large porous and excellent hydrophilicity was obtained successfully. The obtained Tb-MOF was filled into the Nafion matrix to improve its proton conduction performance. The Tb-MOF/Nafion composite membrane was characterized by PXRD, IR, and thermogravimetry (TG) and for water uptake, area swelling, and proton conductivity. The activity energy, Ea, value of the composite membrane, which is a very important factor affecting the proton conduction performance of the membrane, was fitted and calculated. It was revealed that Tb-MOF can improve the proton conductivities of composite membranes, and the improvement degree and Ea value were both affected by Tb-MOF content. When Tb-MOF content was 5%, the proton conductivity of the composite membrane was 1.53 × 10-2 S·cm-1 at 100% RH and 80 °C, which is 1.81 times that of the pure Nafion membrane. A MOF containing a nitro functional group was first doped into Nafion in this study and exhibited excellent performance for improving composite membrane proton conductivity. This study will provide a valuable reference for designing different functionalized MOFs to promote the proton conductivities of proton exchange membranes.

3D Boranil Complexes with Aggregation-Amplified Circularly Polarized Luminescence.

The development of small organic CPL-active molecules with large luminescent dissymmetry factors is highly demanded due to their promising applications in chiroptical devices and sensors. This work describes the design and synthesis of a new family of CPL-active BF2 complexes, (Rp)/(Sp)-3a-3e, which were constructed by fusing a N̂O-chelated BF2 complex with [2.2]paracyclophane. These complexes display aggregation-amplified CPL with moderate dissymmetry factors values and moderate quantum yields both in solution and in the solid state. In addition, these photophysical properties were rationalized via X-ray diffraction and TD-DFT calculations.

Multiresponsive Luminescent Sensitivities of a 3D Cd-CP with Visual Turn-on and Ratiometric Sensing toward Al3+ and Cr3+ as Well as Turn-off Sensing toward Fe3.

By using the reduced Schiff base tricarboxylate ligand H3cip, one novel 3D Cd-based coordination polymer (Cd-CP) with the formula [Cd(Hcip)(bpea)0.5(H2O)]n (H3cip = 5-(3-carboxybenzylamino)isophthalic acid, bpea = 1,2-bis(4-pyridyl)ethane) has been solvothermally synthesized. The prepared Cd-CP possesses a 4-connected CdSO4 net based on dinuclear {Cd2} units. Luminescence measurements revealed that the complex exhibited ratiometric turn-on luminescence responses toward Al3+ and Cr3+ with a significant color change, which could be easily distinguished by the naked eye under ultraviolet light. Cd-CP can also respond to Fe3+ through a turn-off mechanism. Interestingly, the luminescence quenched by Fe3+@Cd-CP can be recovered and increased significantly by adding some competitive Al3+, while Cr3+ can only marginally increase the luminescence intensity of Fe3+@Cd-CP. Moreover, the detection of the three aforementioned metal ions can be realized by using Cd-CP-coated test papers, extending the potential application regions of the reported material to point-of-care tests and environmental field studies.

Postsynthetic Metalation Metal-Organic Framework as a Fluorescent Probe for the Ultrasensitive and Reversible Detection of PO43- Ions.

The self-assembly of a zinc salt with the novel ligand 4,4',4″-[(1,3,5-triazine-2,4,6-triyl)tris(sulfanediyl)]tribenzoic acid generated 3D microporous metal-organic frameworks (MOFs), namely, {[Zn4(L3-)2(O2-)(H2O)2]·4EtOH} n. The frameworks with multiple Lewis basic sites exhibit easily sensitized properties. After encapsulation of the Tb3+ cation in this Zn-MOF, the as-obtained fluorescent-functionalized Tb@Zn-MOFs not only maintain distinguished chemical stabilities but also exhibit strong characteristic emissions of trivalent terbium ions. Interestingly, Tb@Zn-MOF has been chosen to be a potential highly selective and sensitive luminescent platform for the reversible detection of PO43- ions in aqueous and living cell buffer solutions with a fast response time of 10 s and a low detection limit (0.1 ppm). Strikingly, this work presents the first example of a fluorescent sensor that can quantitate PO43- in simulated biological fluids and monitor these ions in the water system in a wide range of concentrations from 10-6 to 10-3 M.

Double-stranded metallo-triangles: from anion-templated nonanuclear to cation-templated tetraicosanuclear dysprosium clusters.

Two double-stranded metallo-triangles, Dy9 and Dy24, with hexaple-C10H7PO32- bridges were constructed, and their magnetic properties were explored. Compared with the field-induced relaxation phenomenon of Dy9 templated with a chloride anion, Dy24 templated with a sodium cation exhibited zero-field single-molecule-magnet behavior.

A simple MOF constructed using Pb(II) with strong polarizing force: a filler of Nafion membrane to increase proton conductivity.

Metal-organic frameworks (MOFs) are promising competitive candidates as fillers for Nafion proton exchange membrane (PEM). Increasing efforts have been made to explore methods for synthesizing MOF fillers and the mechanism by which MOF doping improves the proton conductivity (σH+) values of composite membranes. In this study, a Pb(II) cation with strong polarizing force was selected for the hydrothermal reaction with a simple sulfoterephthalate ligand (H3L). Pb-MOF [Pb2L(OH)]n was obtained, which was constructed using Pb-O layers and deprotonated sulfoterephthalate L3- and exhibited good thermal and water stability. Different amounts of Pb-MOF particles were doped into Nafion to fabricate Pb-MOF/Nafion-x composite membranes, which were characterized using SEM, PXRD, IR spectroscopy, TGA, and other methods. It was found that doping Pb-MOF can apparently improve the water absorbability and thermal stability of the composite membrane. The σH+ of the Pb-MOF/Nafion-7 composite membrane was the highest and 2.14 times that of the pure Nafion membrane at 353 K. The higher proton conduction properties may be explained by the strong polarization force, and Pb(II) cations on the surface of Pb-MOF can decrease the bond energy of the O-H bond of absorbed water molecules and increase the acidity of the composite membrane. The phenomena in this study and our previous study confirm that acidity is the most important factor in favor of proton conductivity.

AIE-active aurones for circularly polarized luminescence and trace water detection.

AIE-active phenyl- and [2.2]paracyclophanyl-based aurones (2-Ph and 2-PCP) were synthesized and investigated with different structures and photophysical properties. The results illustrated that the PCP ring can provide chirality, electron-donating ability and steric hindrance. Accordingly, (Rp)/(Sp)-2-PCP exhibit high sensitivity in trace water detection and aggregation-induced CPL with enhanced quantum yields and luminescence dissymmetry factors.

[5]Helicene-based chiral triarylboranes with large luminescence dissymmetry factors over a 10-2 level: synthesis and design strategy via isomeric tuning of steric substitutions.

Constructing chiral luminescent systems with both large luminescence dissymmetry factor (glum) and high luminous efficiency has been considered a great challenge. We herein describe a highly efficient approach to sterically stabilize the helical configurations of carbo[5]helicenes for improved CPL properties in a series of π-donor and π-acceptor substituted [5]helicenes (1, 2, 3, 4 and 5). Enabled by the ortho-installation of methyl groups as well as the steric effects of triarylamine (Ar3N) and triarylborane (Ar3B) handles in meta-substituted [5]helicenes, their optical resolution into enantiomers has been accomplished using preparative chiral HPLC. The molecular chirality of [5]helicenes can be transferred to Ar3B and Ar3N as light emitters, which allowed further investigations of their chiroptics, including optical rotation, circular dichroism (CD) and circularly polarized luminescence (CPL). Remarkably, 4 has been demonstrated to display dramatically enhanced CPL performance with a much larger glum (>1.2 × 10-2) and an increased emission quantum efficiency (ΦS = 0.75) compared with the other analogues, as a result of the isomeric tuning of substitutions with differential steric and electronic effects. These experimentally observed CPL activities were rationalized by TD-DFT computations for the angle (θµ,m) between electric and magnetic transition dipole moments in the excited states. In addition, the conspicuous intramolecular donor-acceptor charge transfer led to thermal responses in the emissions of 2 and 4 over a broad temperature range.

Ring-forming transformation associated with hydrazone changes of hexadecanuclear dysprosium phosphonates.

{Dy16(µ6-C10H7PO3)2(µ5-C10H7PO3)8(spch)8(µ3-OH)2(µ2-OH)2(µ2-AcO)6(µ3-COO)2(DMF)2(H2O)6}·0.5CH3OH·4.5H2O (1) and {Dy16(µ5-C10H7PO3)4(µ3-C10H7PO3)12(µ2-C10H7PO3H)8(opch)4(DMF)8(MeOH)4}·2.5CH3OH·3H2O (2), where H2spch is ((E)-N'-(2-hydroxybenzylidene)pyrazine-2-carbohydrazide, C10H7PO3H2 is 1-naphthylphosphonic acid and H2opch is (E)-N'-(2-hydroxy-3-methoxybenzylidene)pyrazine-2-carbohydrazide, were successfully synthesized by varying the hydrazone ligands in the Dy-phosphonate system. It is important that the ellipsoidal core experiences a ring forming structural transformation to the supramolecular square motif upon the incorporation of an ortho-methoxy substituent into the hydrazone. Alternating-current (ac) magnetic susceptibility studies of 1 and 2 suggest that similar single molecule magnet behaviors occur for these two complexes. The result represents an effective molecular assembly tactic to develop highly complicated lanthanide coordination clusters through the multicomponent self-assembly of the coalescence of phosphonate- and hydrazone-based ligands and metal salts.

Modulating the relaxation dynamics of the Na2Mn3 system via an auxiliary anion change.

This paper reports two closely related heteropentanuclear manganese complexes, namely, {Na2Mn3(opch)3(µ4-O)(µ2-N3) (µ2-AcO)(µ2-MeO)}·6CH3OH·0.5H2O (1) and {Na2Mn3(opch)3(µ4-O)(µ2-N3)2(µ2-AcO)}·2.5CH3OH·2H2O (2), where H2opch is (E)-N'-(2-hydroxy-3-methoxybenzylidene)pyrazine-2-carbohydrazide. Single-crystal X-ray diffraction analysis reveals that the trigonal bipyramidal skeletons in both complexes are comparable, where a perfect triangular Mn3 motif occupies the equatorial plane. Magnetic investigations suggest that overall antiferromagnetic coupling is present within the triangles of 1 and 2. However, their dynamic magnetic properties are drastically distinct. Indeed, complexes 1 and 2 show two kinds of dual slow magnetic relaxation processes that correspond to anisotropy barriers (Δ) of 9.2 cm-1 (11.4 cm-1 for 2) and 12.8 cm-1 (30.0 cm-1 for 2) for the low- and high-frequency domains, respectively. More importantly, a further comparative study of the structure and magnetism indicates that the coordination sphere of these two model complexes with the homologous hydrazone-based coordination sites undergoes an alteration from methoxide-O to azide-N upon a subtle change of the auxiliary anion accompanied by modulating octahedron geometries, leading to a further influence on different relaxation dynamics.

Single-crystal-to-single-crystal transformations among three Mn-MOFs containing different water molecules induced by reaction time: crystal structures and proton conductivities.

Three Mn-MOFs {[Mn3(µ4-L)2(H2O)7]·4H2O}n (1), {[Mn3(µ5-L)2(H2O)6]·4H2O}n (2) and {[Mn3(µ7-L)2(H2O)2]}n (3) (H3L = 5-(6-carboxypyridin-3-yl)isophthalic acid) were obtained under different reaction times and temperatures. Interestingly, induced by reaction time, compound 1 can lose one water molecule and SC-SC transform into compound 2. Similarly, compound 2 can also SC-SC transform into 3. Studies on two SC-SC transformation processes were carried out and the transformation mechanisms were deduced, which were verified by TG analyses. Different numbers of water molecules in the three compounds resulted in different coordination environments of the metal cation, coordination modes of the L3- ligand, continuities of hydrogen bonds, dimensions of framework and porosities. The AC impendence spectra studies revealed that compounds 1-3 can enhance the proton conductivities of the Nafion composite membrane to about 47.77%, 36.88% and 21.28%, respectively. It is speculated that the highest proton conductivity of compound 1 may be due to its continuous hydrogen bond chain and highest water uptake, which were mainly decided by the number of water molecules.

Poly[[diaqua-(µ(4)-l-tartrato)(µ(2)-l-tartrato)dizinc(II)] tetra-hydrate].

In the title compound, {[Zn(C(4)H(4)O(6))(H(2)O)]·2H(2)O}(n), the l-tartrate ligands adopt µ(4)- and µ(2)-coordination modes. The Zn(II) atom adopts an octa-hedral geometry and is chelated by two kinds of l-tartrate ligands through the hydr-oxy and carboxyl-ate groups and coordinated by one unchelating carboxyl-ate O atom and one water mol-ecule. In the crystal, the l-tartrate ligands link the Zn(II) atoms, forming a two-dimensional coordination layer; these layers are futher linked into a three-dimensional supra-molecular network by O-H⋯O hydrogen bonds between the two-dimensional coordin-ation layers and the uncoordinated water mol-ecules. The latter are equally disordered over two positions.

Consecutive one-/two-step relaxation transformations of single-molecule magnets via coupling dinuclear dysprosium compounds with chloride bridges.

The double chloride-bridged dimer of a dinuclear dysprosium(iii) single-molecule magnet (SMM) was successfully isolated by assembling centrosymmetric dinuclear Dy2 SMMs. Such structural transformation involves the generation and cleavage of chloride bridges and leads to consecutive transformations of one- and two-step slow relaxation of magnetization.

Electrical, optical, thermoelectric power, and dielectrical properties of organic semiconductor poly(1,12-bis(carbazolyl) dodecane) film.

Electrical conductivity, optical, thermoelectric, and dielectrical properties of the poly(1,12-bis(carbazolyl) dodecane) film have been investigated. The activation energy for electrical conductivity and room-temperature electrical conductivity (at 25 degrees C) values were found to be 0.25 eV and 2.65 x 10-6 S/cm, respectively. The thermoelectric power results suggest that the conductivity is due to large polarons (i.e., the carriers in polymer move by hopping in the localized states at band gap edges). Electrical conductivity and thermoelectric power results confirm that the polymer is a p-type organic semiconductor. Optical absorption results suggest that the direct allowed transitions are dominant in the fundamental absorption edge in the polymer with optical band gap value of 2.72 eV. The refractive index dispersion of the polymer obeys the single oscillator model with oscillator energy (Eo = 3.06 eV) and dispersion energy (Ed = 17.82 eV) values. Alternating current conductivity results suggest that the hopping conductivity is dominant in the polymer. The dielectrical properties exhibit a non-Debye relaxation.

An azide-bridged copper(II) complex: poly[piperazine-1,4-dium [tetra-µ3-azido-κ¹²N¹:N¹:N¹-hexa-µ2-azido-κ¹²N¹:N¹-di-µ2-azido-κ4N¹:N³-pentacopper(II)] tetrahydrate].

A new Cu(II)-azide complex, {(C4H12N2)[Cu5(N3)12]·4H2O}n, has been synthesized by the reaction of piperazine, Cu(OAc)2·2H2O (OAc is acetate) and NaN3. In the structure, µ2-1,1- and µ3-1,1,1-azide anions bridge five Cu(II) cations to form a linear pentanuclear cluster unit, which is further linked by µ2-1,1- and µ2-1,3-azide anions to form a two-dimensional condensed [Cu5(N3)12]n layer. The diprotonated piperazine and the solvent water molecules are hydrogen bonded to the coordination layers to form a three-dimensional supramolecular network.

Topological ferrimagnetic behaviours of coordination polymers containing manganese(II) chains with mixed azide and carboxylate bridges and alternating F/AF/AF'/AF'/AF interactions.

Two Mn(ii) complexes with azide and a new zwitterionic tetracarboxylate ligand 1,2,4,5-tetrakis(4-carboxylatopyridinium-1-methylene)benzene (L(1)), {[Mn5(L(1))2(N3)8(OH)2]·12H2O}n () and {[Mn5(L(1))2(N3)8(H2O)2](ClO4)2·6H2O}n (), have been synthesized and characterized crystallographically and magnetically. and contain similar alternating chains constructed by azide and carboxylate bridges. The independent sets of bridges alternate in an ABCCB sequence between adjacent Mn(ii) ions: (EO-N3)2 double bridges (EO = end-on) (denoted as A), [(EO-N3)(OCO)2] triple bridges (denoted as B) and [(EO-N3)(OCO)] double bridges (denoted as C). The alternating chains are interlinked into 2D coordination networks by the tetrapyridinium spacers. Magnetic studies demonstrate that the magnetic coupling through the double EO azide bridges is ferromagnetic and that through mixed azide/carboxylate bridges is antiferromagnetic. The unprecedented F/AF/AF'/AF'/AF coupling sequence along the chain dictates an uncompensated ground spin state (S = 5/2 per Mn5 unit) and leads to one-dimensional topological ferrimagnetism, which features a minimum in the χT versus T plot.