Aggregation-induced emission enhancement (AIEE) of tetrarhenium(I) metallacycles and their application as luminescent sensors for nitroaromatics and antibiotics.

The self-assembly of tetrarhenium metallacycles [{Re(CO)3}2(µ-dhaq)(µ-N-N)]2 (3a, N-N = 1,3-bis(1-butylbenzimidazol-2-yl)benzene; 3b, N-N = 1,3-bis(1-octylbenzimidazol-2-yl)benzene), (H2-dhaq = 1,4-dihydroxy-9,10-anthraquinone) and [{Re(CO)3}2(µ-thaq)(µ-N-N)]2 (4, N-N = 1,3-bis(1-butylbenzimidazol-2-yl)benzene), (H2-thaq = 1,2,4-trihydroxy-9,10-anthraquinone) under solvothermal conditions is described. The metallacycles 3a,b and 4 underwent aggregation-induced emission enhancement (AIEE) in THF upon the incremental addition of water. TEM images revealed that metallacycle 3a in a 60% aqueous THF solution formed rectangular aggregates with a wide size distribution, while a 90% aqueous THF solution resulted in the formation of a mixture of nanorods and amorphous aggregates due to rapid and abrupt aggregation. UV-vis and emission spectral profiles supported the formation of nanoaggregates of metallacycles 3a,b and 4 upon the gradual addition of water to a THF solution containing metallacycles. Further studies indicated that these nanoaggregates were excellent probes for the sensitive and selective detection of nitro group containing picric acid (PA) derivatives as well as antibiotics.

Pd-Promoted Cyclization of (Z)-Pent-2-en-4-yn-1-yl Alkanoates Leading to Furans via an Acyl Group Shift and Further Synthetic Transformation.

Palladium-promoted acyl migration was observed in the reaction of (Z)-pent-2-en-4-yn-1-yl alkanoates in the presence of DBU to yield 2-(alkanoylmethyl)furan derivatives (2) in high yields. Compounds 2 then underwent oxidative decarbonylation to afford 2-acylfurans with O2 as the oxidant under mild and metal-free conditions. The mechanistic pathway of the reaction involving an intramolecular cyclization and acyl group shift is discussed.

Porous Supramolecular Assembly of Pentiptycene-Containing Gold(I) Complexes: Persistent Excited-State Aurophilicity and Inclusion-Induced Emission Enhancement.

We report herein a porous supramolecular framework formed by a linear mononuclear Au(I) complex (1) via the tongue-and-groove-like joinery between the pentiptycene U-cavities (grooves) and the rod-shaped π-conjugated backbone and alkyl chains (tongues) with the assistance of C-H···π and aurophilic interactions. The framework contains distorted tetrahedral Au4 units, which undergo stepwise and persistent photoinduced Au(I)-Au(I) bond shortening (excited-state aurophilicity), leading to multicolored luminescence photochromism. The one-dimensional pore channels could accommodate different solvates and guests, and the guest inclusion-induced luminescence enhancement (up to 300%) and/or vapochromism are characterized. A correlation between the aurophilic bonding and the luminescence activity is uncovered by TDDFT calculations. Isostructural derivatives 2 and 3 corroborate both the robustness of the porous supramolecular assembly and the mechanisms of the stimulation-induced luminescence properties of 1. This work demonstrates the cooperation of aurophilicity and structural porosity and adaptability in achieving novel supramolecular photochemical properties.

Palladium-Catalyzed Vinylation of Cyclopentenes with Inverted Z,E-Isomerism of Vinylic Substrates.

A palladium-promoted Mizoroki-Heck type reaction employing a directing-group strategy to efficiently produce the coupled vinyl cyclopentenes with excellent regio- and stereoselectivity is reported. Typically, a Pd-catalyzed reaction of 2-(cyclopent-2-en-1-yl)-N-tosylacetamide (1a) with (E)-styryl bromides gave cis-2-((Z)-styryl)cyclopent-3-en-1-yl-N-tosylacetamide (3e), an allylic substitution product. Interestingly, we have found that the E,Z-stereochemistry of vinylic substrates is inverted in those products. The mechanism of this catalytic reaction is discussed.

Metal-Ion-Induced Mechanical Chirality: Achiral Rotaxane as the Only Ligand in Chiral Palladium(II)-N-Heterocyclic Carbene Complexes.

We report the insertion of Pd(II) into an originally achiral rotaxane producing two chiral metallorotaxanes: one is planar-chiral, with its two interlocked components both chelating nonequivalently to the metal center; the other is C2-symmetrical-chiral, with the dynamically exchangeable stereogenic units stabilized by the interlocked structure. Chiral additives confirmed the existence of chirality, with the enantiomers of the C2-symmetrical N-heterocyclic carbene complex being resolved using chiral TRISPHAT counteranions.

Complementarity of 2,6-Dimethanolpyridine and Di(ethylene glycol) in the Complexation of Na+ Ions: Attaching Multiple Copies of [2]Catenane Branches to Isophthalaldehyde-Containing Cores.

In this study we found that 2,6-dimethanolpyridine displays good complementarity toward di(ethylene glycol) for the complexation of Na+ ions, allowing us to use this recognition system for the efficient synthesis of hetero[2]catenanes; indeed, it allowed us to attach multiple copies of [2]catenanes to branched systems presenting multiple isophthalaldehyde units. When we attempted to form a catenane from a preformed macrocycle featuring only a single di(ethylene glycol) unit, reacting it with a di(ethylene glycol) derivative presenting two amino termini, isophthalaldehyde, and templating Na+ ions [i.e., with the aim of using di(ethylene glycol)·Na+·di(ethylene glycol) recognition to template the formation of the interlocked imino macrocycle], the yields of the hetero[2]catenane and homo[2]catenane, comprising two imino macrocyclic units, were both poor (14% and 7%, respectively). In contrast, when one or two 2,6-dimethanolpyridine units were present in the preformed macrocycles, their reactions with the same diamine, dialdehyde, and Na+ ions provided the hetero[2]catenanes with high selectivity and efficiency (44% and 64% yields, respectively), with minimal formation of the competing homo[2]catenane. The high complementary of the 2,6-dimethanolpyridine·Na+·di(ethylene glycol) ligand pair allowed us to synthesize [2]catenane dimers and trimers directly from corresponding isophthalaldehyde-presenting cores, with yields, after subsequent reduction and methylation, of 42% and 31%, respectively.

A new series of heteronuclear metal strings, MRhRh(dpa)4Cl2 and MRhRhM(dpa)4X2, from the reactions of Rh2(dpa)4 with metal ions of group 7 to group 12.

We report the syntheses, structures, magnetic and electrochemical properties of MRhRh metal cores helically wrapped by four dpa- (2,2'-dipyridylamide) ligands. We successfully synthesized the precursor Rh2(dpa)4 (1) in high yield and characterized its structure including its oxidized form (1+) which facilitated the syntheses of this series of metal springs. By the reactions of (1) and the metal ions of group 7 to group 12 (M = Mn(2), Fe(3), Co(4), Ni(5), Cu(6), Pd(8), Pt(9), Ru(10), Ir(11) and Rh(12)), ten MRh2(dpa)4Cl2 complexes were successfully isolated. Note that Cd(7) can only be obtained by the one-pot method. The yield of Rh3(dpa)4Cl2 (12) is also improved by this stepwise method. The oxidized complexes [MRh2(dpa)4Cl2](PF6) (M: Ni(5+), Ru(10+), Ir(11+)) are also synthesized for the studies of electronic structures and magnetic properties. The X-ray diffraction technique is applied to characterize all of their structures. The results of these structural, magnetic, and electrochemical studies provide us with in-depth knowledge and comprehensive insight into metal-metal bonds and interactions for this new series of metal strings. In particular, four metal-metal bonds with short distances are found: Pd-Rh (2.372(13) Å), Pt-Rh (2.385(7) Å), Ru-Rh (2.33(3) Å), and Ir-Rh (2.373(5) Å). The remaining ones show no evidence of covalent metal bonds judging from their metal-metal distances, magnetic behaviour, and redox couples in electrochemical analysis. Besides, two unique tetranuclear MRhRhM(dpa)4X2 (M: Cu+(13) and Ag+(14)) complexes with a Rh2(dpa)4 framework are developed. Four metals are aligned linearly. This coordination mode of metal strings provides a unique synthetic route for constructing longer metal chains from a smaller number of dentate ligands.

A polymorphic pentiptycene-containing gold(I) isocyanide complex: solvent- and conformation-dependent supramolecular luminescence.

Four crystalline (pseudo)polymorphs of [Ph-Au-C[triple bond, length as m-dash]N-Phip-OC8H17] (1), where Phip = central phenylene of pentiptycene, reveal that the π-backbone conformation relative to the AuAu bonding axis is important in determining the energy and efficiency of the supramolecular luminescence, which offers mechanistic insights into the luminescence mechanochromism and vapochromism and the solvent-dependent aggregation-induced emission (AIE) of 1.

Steric Engineering of Cyclometalated Pt(II) Complexes toward High-Contrast Monomer-Excimer-Based Mechanochromic and Vapochromic Luminescence.

Ligands play a crucial role in the supramolecular photoluminescence properties of Pt(II) square-planar complexes. To improve the luminescence color responses of N∧C∧N cyclometalated Pt(II) complexes to external stimuli such as mechanical stress and chemical vapors, we have conducted a steric engineering of the previous systems 1a-1d [Inorg. Chem. 2017, 56, 4978-4989] by introducing two tert-butyl groups to the tridentate ligand to form complexes 2a-2c. Unlike the "too low" or "too high" steric hindrance of the NCNPt core in 1a-1d, the combined steric effects of the tert-butyl groups at one side and the pentiptycene group at the other side of the NCNPt core in 2b are "just right" for generating as-prepared powders with pure monomer (green) emission or pure excimer (red) emission, depending on the rate of precipitation from solutions. The synergistic steric effects are also beneficial to the solid-state luminescence quantum efficiency (30-36%). As a result of the differences in steric interactions and thus in the relative monomer vs excimer emission intensity, each complex of 2a-2c performs a two-step luminescence mechanochromism and vapochromism with different color patterns. This work provides an intriguing example of steric engineering of Pt(II) complexes toward highly emissive molecular solids with high-contrast mechanochromic and vapochromic luminescence.

Study of Electronic and Vibrational Structures of Reduced, Neutral, and Oxidized Ni3(dpa)4X2 Using Density Functional Theory and Raman Spectroscopy.

The electronic and vibrational structures of trinickel metal string complexes [Ni3(dpa)4X2]1-,0,1+ (X = Cl, NCS) were investigated using both theoretical calculations and spectroscopic methods. We used the density functional theory (DFT) method B3LYP*-D3, including less exact exchange energy and the van der Waals interaction of metal ions, to obtain the geometries and vibrational structures, which were found to be in excellent agreement with the experimental data. The ground state of Ni3(dpa)4X2 is an antiferromagnetic (AF) singlet state, and the next state is a quintet state, which was detected using temperature-dependent Raman spectroscopy under a magnetic field. The vibrational structure of the quintet state is nearly identical to that of the AF state, according to the measured Raman spectra, except that the stretching of Ni-Cl is blue-shifted from 282.5 cm-1 in the AF state to 283.8 cm-1 in the quintet state. Two oxidized Ni3 complexes were found to have [Ni3]7+ cores, the doublet [Ni3(dpa)4]3+ without axial ligands and the quartet [Ni3(dpa)4X2]+. Complex [Ni3(dpa)4X2]-, which was produced from a reduction reaction by gold nanoparticles at room temperature, consists of a quartet state as the ground state and a doublet state lying nearby.

A frontier Zn- and N-rich complex grafted onto reduced graphene oxide for the electrocatalysis of dye-sensitized solar cells.

This paper proposes a novel µ-hydroxo-bridged dinuclear macrocyclic zinc complex, {[Zn(C10H20N8)]2(OH)}(BF4)3. The structure was determined by X-ray crystallography: Monoclinic, C2/c, a = 25.4632(6), b = 10.9818(3), c = 15.7522(4) Å, Z = 8, R1 = 0.0233, wR2 = 0.0557, based on reflections I > 2σ(I). The complex was successfully reacted with graphene oxide to form a µ-hydroxo-bridged dinuclear macrocyclic Zn complex/reduced graphene oxide composite. To evenly disperse the Zn- and N-rich complex onto the surface of the reduced graphene oxide, and to enhance the electrocatalytic property of the graphene composites, a soluble molecular grafting method was used here. The graphene-based composites were applied as the counter electrodes (CEs) of dye-sensitized solar cells. Current density-voltage measurements revealed that the conversion efficiency of the GO/Zn (1 : 10) sample was 7.78%, which was better than that of Pt CE (7.49%). GO/Zn (1 : 10) CE exhibited the lowest impedance (RCE = 9.90 Ω), which was better than that of Pt CE (RCE = 66.1 Ω), showing that GO/Zn CEs can reduce the impedance at the CE/electrolyte interface. The proposed method is simple, and the composite materials can potentially replace conventional Pt, optimizing efficiency and reducing production cost.

Structure and magnetic properties of a novel heteroheptanuclear metal string complex [Ni3Ru2Ni2(µ7-teptra)4(NCS)2](PF6).

We report the synthesis of a novel heteroheptanuclear metal string complex (HMSC) [Ni3Ru2Ni2(µ7-teptra)4(NCS)2](PF6) 1 supported by tetra-pyridyl-tri-amine (H3teptra) ligands. We employed X-ray diffraction and other spectroscopic techniques to characterize the complex. The observed remarkably short Ru-Ru distance of 2.2499(3) Å for 1 is indicative of a unique metal-metal interaction in the mixed-valence [Ru2]5+ (S = 3/2) unit. The complex exhibits a relatively high magnetic moment value of 4.55 B.M. at 4 K, which increases rapidly to 6.00 B.M. at 30 K and remains at 6.11 B.M. from 50 to 300 K as shown by SQUID measurements, indicating a high spin (S≥ 3/2) system which is further supported by the analyses of EPR spectra at low temperatures. These magnetic behaviors can be ascribed to the result of spin-exchange interactions among multi-spin centers.

Interlocking increases the persistence of N-heterocyclic carbenes in solution.

In this study imidazolium and imidazolinium centers in precursor [2]rotaxanes were deprotonated to obtain interlocked molecules featuring stabilized N-heterocyclic carbene centers. The encircling macrocyclic components enhanced the persistence of the otherwise unstable imidazolidin-2-ylidenes in solution at 253 K for more than a week in the absence of air.

Structures and paramagnetism of five heterometallic pentanuclear metal strings containing as many as four different metals: NiPtCo2Pd(tpda)4Cl2.

Five heterometallic pentanuclear metal strings were prepared by stepwise synthesis from two to three and four kinds of metals aligned in one chain. In particular, NiPtCo2Pd(tpda)4Cl2 (5) possesses four different metals, and the SQUID measurement shows that Ni2+ is the only magnetically active center. Besides, the shortest Co(ii)-Co(ii) single bond (2.105(9) Å), so far, is reported.

Alkyl Chain Length- and Polymorph-Dependent Photomechanochromic Fluorescence of Anthracene Photodimerization in Molecular Crystals: Role of the Lattice Stiffness.

Anthracene-pentiptycene hybrid systems 1-Cn, where n refers to the number of carbon atoms in the linear alkyl chain, crystallize in three different polymorphs, denoted Y (yellow), G (green), and B (blue) forms in terms of the fluorescence color. While all Y-form crystals show the same yellow-to-blue fluorescence color response to the photomechanical stress generated by the anthracene [4+4] photodimerization reaction, the four G forms exhibit distinct photomechanofluorochromism (PMFC): from green to blue for G-1-C4, to orange for G-1-C7, to red for G-1-C8, and to red then blue for G-1-C9, and the B forms show no photochromic activity. The intriguing RGB three-color PMFC and abnormal topochemical reactivity of G-1-C9 are attributed to inherent softness of the crystal lattice.

N-Heterocyclic Carbene Copper(I) Rotaxanes Mediate Sequential Click Ligations with All Reagents Premixed.

We have prepared NHC-CuI complexes with a rotaxane structure and used them as sterically sensitive catalysts for one-pot sequential copper-catalyzed azide/alkyne cycloadditions in solutions containing all of the coupling partners premixed in unprotected form. Most notably, a photolabile and sterically encumbered complex first catalyzed the coupling of a less bulky azide/alkyne pair; after removing the protective macrocyclic component from the rotaxane structure, through irradiation with light, the exposed dumbbell-shaped NHC-CuI complex catalyzed the second click reaction of a bulkier azide/alkyne pair. Using this approach, we obtained predominantly, from a single sealed pot, a bis-triazole product (84 %) from a mixture of two sterically distinct azides and a diyne.

Zinc(II)-Organic Framework Films with Thermochromic and Solvatochromic Applications.

Multiple-stimuli-responsive photoluminescence films based on a ZnII -organic framework, {[Zn2 (Htpim)(3,4-pydc)2 ]⋅4 DMF⋅4 H2 O}n (1, Htpim=2,4,5-tri(4-pyridyl)imidazole, 3,4-H2 pydc=3,4-pyridinedicarboxylic acid), were fabricated. This compound consisted of a 2D corrugated layer, {Zn(3,4-pydc)}n , which was further pillared using a Y-shaped pillar N-donor ligand (Htpim) to form a 3D-pillared-layer framework with 1D open channels. The rectangular channels in the as-synthesized compound are fully occupied by guest DMF and H2 O molecules. The framework exhibits instant and reversible thermochromic properties corresponding to the removal of different H2 O and DMF guest molecules as temperature increases. The pale-yellow crystal undergoes significant redshifting to a greenish emission centered at 530 nm. Compound 1 also showed remarkable solvatochromic effects in the presence of various organic solvents without affecting its structural integrity. In addition, polycrystalline MOF films were grown on an α-Al2 O3 support for switchable and fast-response thermochromic and solvatochromic sensors.

Synthesis of 2-arylamino-3-cyanoquinolines via a cascade reaction through a nitrilium intermediate.

A new method for the preparation of 2-amino-3-cyanoquinolines from readily available aryldiazonium salts, 2-aminoarylketones, and malononitrile via a cascade reaction is reported. This one-pot approach involves the in situ generation of an N-arylnitrilium intermediate from the direct reaction of aryldiazonium salts and malononitrile, which undergoes intermolecular amination, Knoevenagel condensation, and then aromatization to yield the desired compound in moderate to good yields. This methodology features a quick assembly of C2 and C3 functionalized quinolines.

Facet-Dependent Reduction Reaction of Diruthenium Metal-String Complexes by Face-to-Face Linked Gold Nanocrystals.

The facet-dependent redox reactions of diruthenium metal-string complexes by gold nanoparticles (AuNPs) are explored by using the surface-enhanced Raman scattering (SERS) technique. Gold nano-rhombic dodecahedrons (AuRDs), gold nanocubes (AuNCs), and gold octahedrons (AuOhs) with exclusive facets {110}, {100}, and {111}, respectively, were synthesized. These AuNPs linked face-to-face by metal-string complexes Ru2M(dpa)4Cl2 (dpa = dipyridyl amino, M = Ni, Cu) with chloride axial ligands serve as both SERS substrates and reducing agents in the reactions. We employ the diruthenium core in these complexes with multiple redox states to study the reduction ability of varied AuNP facets upon plasmonic excitation. In Ru2Ni(dpa)4Cl2, the Ru-Ru stretching mode νRu-Ru str. lies at 327 cm-1 on the SERS substrate AuOh, but this band shifts to 313 cm-1 on the AuRD and AuNC. The diruthenium moiety was reduced to [Ru2]4+ by the AuRD facet {110} and the AuNC {100}. The gold nanorods in the solution prepared with metal-string complexes bridging head-to-head on {111} facets were used for the SERS substrate. The SERS curves of the complexes in these self-assembled head-to-head rods display νRu-Ru str. at 327 cm-1, which is assigned to having an [Ru2]5+ core. Hence, facets {110} and {100} have a reduction reactivity greater than that of {111}. In Ru2Cu(dpa)4Cl2, the νRu-Ru str. is observed to lie at 312 cm-1 on AuRD, but shifts to 320 cm-1 on the AuNC and AuOh. In the latter cases, the diruthenium moiety was reduced to having a charge of 4+ with electronic configuration π*2δ*2, whereas the former case band at 312 cm-1 with a weaker Ru-Ru bonding is also attributed to [Ru2]4+ but with electron configuration π*4. π*4 lies at an energy greater than π*2δ*2. The electrochemical SERS spectra of diruthenium complexes were recorded to verify their oxidation states. Conclusively, these results yield the reduction reactivity of the following facet: {110} > {100} > {111}. According to the results of the redox reactions, the valence states of the diruthenium metal-string complexes are verified. In the [Ru2] n+ core, n = 4 π*4, 4 π*2δ*2, 5 π*2δ*, and 6 π*δ*, and the νRu-Ru str. is 312, 320, 327, and 337 cm-1, respectively.

Facile synthesis of 1,5-disubstituted tetrazoles by reacting a ruthenium acetylide complex with trimethylsilyl azide.

Treatment of [Ru]-C[triple bond, length as m-dash]CPh (1, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with trimethylsilyl azide afforded the cationic nitrile complex {[Ru]NCCH2Ph}[N3] (2) and the further cycloaddition of 2 with trimethylsilyl azide at 60 °C afforded the N(2)-bound tetrazolato complex [Ru]N4CCH2Ph (3). The regiospecific alkylation of 3 gave a series of cationic N(2)-bound N(4)-alkylated-5-benzyl tetrazolato complexes {[Ru]N4(CH2R)CCH2Ph}[Br] (4a, R = C6F5; 4b, R = Ph; 4c, R = 4-CN-C6H4; 4d, R = 2,6-F2-C6H3; 4e, R = 6-CH2Br-C5NH3) and the subsequent cleavage of the Ru-N bond of 4a-4e gave N(1)-alkylated-5-benzyl tetrazoles N4(CH2R)CCH2Ph (5a-5e) in good to excellent yields and [Ru]-Br, which, on reacting with phenylacetylene, resulted in the formation of 1 thus forming a reaction cycle. The structures of 2, 3, 4a, 4c and 5a were confirmed by single-crystal X-ray diffraction analysis.