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An I2-mediated aerobic cyclization reaction of anilines, alkynes, and tertiary amine has been reported. In this protocol, a novel strategy for the synthesis of quinolines using tertiary amines as a C1 synthon via C–N bond cleavage.

A nanoflower-like bimetallic FeP/CoP-1-350 heterostructure electrocatalyst with rich interfaces shows excellent OER electrocatalytic activity.

To develop new anti-metastasis chemotherapeutic drugs, a series of flurbiprofen (FLP) and zaltoprofen (ZTP) platinum(IV) complexes targeting COX-2, PD-L1 and DNA was prepared and investigated. Complex 2 with dual FLP ligands displays promising antitumor activities

Polysaccharides from marine organisms are potential sources of low side-effect and high efficiency anticancer drugs.

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.

{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.

The exploitation of efficient hydrogen evolution reaction (HER) electrocatalysts has become increasingly urgent and imperative; however, it is also challenging for high-performance sustainable clean energy applications. Herein, novel Co9S8 nanoparticles embedded in a porous N,S-dual doped carbon composite (abbr. Co9S8@NS-C-900) were fabricated by the pyrolysis of a single crystal Co-MOF assisted with thiourea. Due to the synergistic benefit of combining Co9S8 nanoparticles with N,S-dual doped carbon, the composite showed efficient HER electrocatalytic activities and long-term durability in an alkaline solution. It shows a small overpotential of −86.4 mV at a current density of 10.0 mA cm−2, a small Tafel slope of 81.1 mV dec−1, and a large exchange current density (J0) of 0.40 mA cm−2, which are comparable to those of Pt/C. More importantly, due to the protection of Co9S8 nanoparticles by the N,S-dual doped carbon shell, the Co9S8@NS-C-900 catalyst displays excellent long-term durability. There is almost no decay in HER activities after 1000 potential cycles or it retains 99.5% of the initial current after 48 h.

Two heterometallic metallacrown complexes, [Er{Cu4(butyrat)4}2]·Cl3·MeOH·26H2O (1) and [Yb{Cu4(butyrat)4}2]·Cl3·MeOH·26H2O (2) (H2butyrat = 3-aminobutyric hydroxamic acid), have been reported. X-ray crystallographic analysis reveals that the two complexes displayed nested-sandwich configurations with two 12-MC-4 metallacrown units capping LnIII in the centre. Magnetic studies revealed that 1–2 undergo antiferromagnetic coupling interaction. Magnetic measurements show that complex 2 displays frequency-dependent signals at a dc field of 1000 Oe, indicating field-induced single-molecule magnet behavior.

Cycloxygenases (COXs) and matrix metalloproteinases (MMPs) in the tumor microenvironment (TME) are tightly related to the progression of cancers. Here, naproxen as a potent inhibitor of both COX and MMP was combined with platinum(iv) to construct hybrids as antitumor agents. Compound 2 with comparable or even superior activities to that of cisplatin, oxaliplatin, and carboplatin, great potential for reversing drug resistance, and superior tumor targeting properties was screened out as a lead compound. Moreover, compound 2 possessed potent tumor growth inhibition capability in vivo, which was comparable to that of oxaliplatin, and displayed rather lower side effects than the platinum(ii) reference drugs. The naproxen platinum(iv) complex could easily undergo reduction and liberate the platinum(ii) complex and naproxen as well as exert a multifunctional antitumor mechanism: (i) the liberated platinum(ii) fragment would cause serious DNA injury; (ii) naproxen would inhibit COX-2 and decrease tumor-associated inflammation; and (iii) the naproxen platinum(iv) complex exhibited remarkable MMP-9 inhibition in tumor tissues. These antitumor functions can help reduce the growth and metastasis of malignancy.

Heterometallic cluster-organic frameworks with fascinating architectures and multi-functionality have the potential to be applied in various fields. However, in comparison with p–d, d–d, and d–f heterometallic cluster-organic frameworks, p–f heterometallic cluster-organic frameworks are far less explored even though they possess multiple merits. Herein, two novel isomorphic 4p–4f heterometallic cluster-organic frameworks based on high-nuclear [Ln11Ge12] (Ln = Pr, L1 and Nd, L2) second building units have been successfully synthesized via a hydrothermal approach by using bis(carboxyethylgermanium) sesquioxide (H2E2Ge2O3, E = –CH2CH2COO–). The [Ln11Ge12] cluster is constructed with two Ln-capped Ge6-rings sandwiching a gear-like [Ln9] unit. The as-prepared 4p–4f heterometallic [Ln11Ge12] cluster-organic frameworks possess two-dimensional (2D) layered structures. Moreover, the property study reveals the selective and sensitive luminescence sensing of Fe3+ with L1, exhibiting its promising application in environmental monitoring.

Six novel heterobimetallic cyanide-bridged complexes formulated as {[Cu(dmpn)2]2[Fe(bpb)(CN)2]}[Fe(bpb)(CN)2](ClO4)2·2H2O (1), [Cu(dmpn)2][Fe(bbp)(CN)3]n·0.5nDMF·2.5nH2O (2), {[Cu(dmpn)2]1.5[Cr(CN)5(NO)]}n·3nH2O (3), {[Cu(dmpn)2]2[Fe(CN)6]}n·10nH2O (4), {[Cu(dmpn)2]4[Mo(CN)8]2}·CH3CN·2H2O (5), and {[Cu(dmpn)2]4[W(CN)8]2}·CH3CN·2H2O (6) (bpb = 1,2-bis(pyridine-2-carboxamido)benzenate, bbp = 2,6-bis(benzimidazoi-2-yl)pyridine, dmpn = 2,2-dimethyl-1,3-diaminopropane, DMF = N,N-dimethylformamide) were synthesized with one amine copper compound as an assembly segment and six polycyanometallates containing two, three, five, six or eight cyanide groups as building blocks. All of the six complexes have been characterized using elemental analysis, IR spectra, and powder and single crystal X-ray diffraction. Structural analysis revealed diverse structural types of complexes 1–6, ranging from discrete polynuclear entities (1) to a 1D single chain (2) to 2D (3, 5 and 6) and 3D (4) networks, clearly indicating the important role of the building block in tuning the structures of the target complexes. The magnetic properties of the reported cyanide-bridged complexes have been experimentally studied and theoretically simulated, disclosing ferro- or antiferromagnetic coupling between the low spin Fe(III) ion and Cu(II) ion and the antiferromagnetic interaction between the Cr(I) ion and the Cu(II) ion through the cyanide bridge. Furthermore, the nature of the magnetic coupling has been analysed based on the magneto-structural correlation.

Assembled from a reduced Schiff base tricarboxylate ligand H3L, two novel Cd-MOFs with the formulae {[Cd(HL)(bpy)]·1.25H2O·1.5DMF}n (LCU-107) and {[Cd(HL)(bpea)·H2O]·H2O·DMF}n (LCU-108) (where LCU stands for Liaocheng University, H3L = 5-(4-carboxybenzylamino)isophthalic acid, bpy = 4,4′-bipyridine, and bpea = 1,2-di(4-pyridyl)ethane), were obtained. LCU-107 possesses a 3D pcu framework based on dinuclear units. LCU-108 demonstrates an interesting 2D → 2D interdigitating and penetrating structure. The flexible carboxylate ligands can all bend in these complexes due to the rotation of –CH2–NH– groups. Luminescence measurements indicated that these two Cd-MOFs show highly selective and sensitive sensing activities toward acetylacetone (acac) and Cr2O72− through a luminescence enhancement and a quenching effect, respectively. The detection limits toward acac are as low as 0.136 and 0.058 ppm, respectively. To our knowledge, these two Cd-MOFs may represent very rare examples of special turn-on acac sensors, as well as being dual-responsive chemosensors for both acac and Cr2O72−.

We have prepared three 3d–4f heterometallic complexes, namely[Ln3Zn3(Hvanox)3(vanox)3(NO3)6(H2O)5]·nEtOH (LnIII = Dy, n = 3 (1), LnIII = Tb, n = 5 (2), LnIII = Er, n = 5 (3)), by the reaction of o-vanillin oxime (H2L) with Zn(NO3)2·6H2O and Ln(NO3)2·6H2O salts in the presence of triethylamine. Single Crystal X-ray diffraction shows Zn ions and Ln ions are linked together to display a windmill-like framework with the dinuclear LnZn(HL)(L) as flabellum. Magnetic measurements reveal that complexes 1 and 2 exhibit field-induced frequency-dependence signals, indicating single-molecule magnetism (SMM) behaviors, while complex 3 exhibits slow magnetic relaxation.

With the careful modulation of the relative ratio of Y3+/Eu3+and Y3+/Tb3+, two series of bimetallic RE-CPs (EuxY1−x and TbxY1−x) were successfully obtained through the isomorphous substitution method. Interestingly, the introduction of Y3+ ions does not change the fluorescence characteristic peak of 1-Eu and 1-Tb, but enhances its fluorescence lifetime and quantum yield. Experimental and theoretical simulation results show the co-doping process changes the intramolecular energy transfer process and reduces the non-radiative transition resulting from concentration quenching. Eu0.1Y0.9 and Tb0.1Y0.9 with the largest luminescence lifetime were selected as the representative research objects, their potential application for the detection of toxic metal ions and organic molecules was further investigated. Interestingly, Eu0.1Y0.9 and Tb0.1Y0.9 demonstrate high sensitivity and good selectivity towards Fe3+, Cr3+ and acetone. Besides, fine fluorescence visibility provides the necessary conditions for the preparation of simple and fast response fluorescent test papers in order to achieve real-time and convenient detection of these toxic materials.

A microporous metal-organic framework functionalized with in situ generated NHC-CuCl units (1) has been successfully synthesized from a novel imidazolium-containing ligand. In particular, the MOF 1 can catalyze β-boration of α,β-unsaturated carbonyl compounds, while the isoreticular version of 1 (1-im) modified with only imidazolium moiety cannot. This work demonstrates for the first time the heterogeneous catalysis of NHC-Cu(i)Cl within a MOF solid.

Simultaneously involving abundant [NH2(CH3)2]+ cations and uncoordinated carboxylate oxygen atoms as dual active sites, two microporous CoII-MOFs (LCU-105 and LCU-106, LCU = Liaocheng University) both exhibit highly selective adsorption of CO2/CH4 and CO2/N2. GCMC theoretical simulations provide good verification of the experimental results.

Two Cd(II) coordination polymers (CPs) were assembled from the mixed ligand strategy of π-conjugated aromatic polycarboxylates and bis(imidazole) linkers, with the structures being a 2-fold interpenetrating 3D bbf net for 1 and a 2D hxl sheet for 2. The fluorescence measurements revealed that both Cd(II) CPs were promising luminescent sensors for the detection of nitrofuran/nitroimidazole antibiotics (ABXs) with low detection limits. Besides, the luminescence quenching of the two Cd(II) CPs toward ABXs was investigated by using DFT calculations and spectral overlap experiments.

A series of cobalt–lanthanide metallacrowns (MCs) {CoIII4Ln8} (Ln = Dy3+1, Ho3+2 and Tm3+3) based on pyrazinehydroxamic acid (H2pyzha) and pyrazinic acid (Hpyzic) ligands have been synthesized. These isomorphous 3d–4f MCs contain two novel [12-MC-4] with –[Co–N–O–Ln]– connectivity to capture one Ln3+ ion in the core of each MC. Two [12-MC-4] units are connected with the central Ln3+ ions forming a butterfly-shaped structure. The existence of this structure leads to a new coordination mode of H2pyzha which has never previously been reported. The magnetic properties of these MCs have been studied and the {CoIII4Dy8} (1) was found to exhibit the single-molecule magnet (SMM) behavior.

Three new luminescent transition coordination polymers, namely, {[Cd(L)(4,4-bpy)]·DMF·H2O}n (1), {[Cd2(L)2(bpe)2]·3DMF·2.5H2O}n (2), and {[Cd(L)(bibp)]·2DMF}n (3), (H2L = 4,4′-[benzene-1,3-diylbis(methanediylsulfanediyl)]dibenzoic acid, 4,4-bpy = 4,4-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene, and bibp = 4,4′-bis(benzoimidazo-1-ly)biphenyl), were solvothermally synthesized using Cd2+ ions and S-containing dicarboxylate acid in the presence of different N coligands. These complexes were fully characterized via elemental analysis, infrared spectroscopy (IR), single crystal X-ray diffraction analysis, and thermal gravimetric analysis (TGA). Complexes 1–3 consist of 2-D structures through the connectivity of similar 1-D Cd-L chains by different N coligands. With an increase in the size of the N coligands, these complexes show structural changes from 2D → 3D with 3-fold interpenetration of complexes 1 and 2 to the 2-D packing modes of complex 3. The luminescence properties of these three complexes were studied in detail. The results reveal that each complex exhibits selectivity and sensitivity towards Fe3+ and Cr2O72− ions, and complex 2 demonstrates the lowest detection limit towards both ions.

Herein, a new family of LnIII[18-metallacrown-6] compounds with the formula [Fe6O2Ln(tBu-sao)6(OH)(MeO)4(MeOH)(H2O)]·6MeOH [Ln = DyIII (1), TbIII (2), GdIII (3), and YIII (4), tBu-saoH2 = 3,5-di-tert-butylsalicylaldoxime] was synthesized through one-pot reactions using tBu-saoH2, Fe(ClO4)3·6H2O, and Ln(NO3)3·6H2O. The four compounds are isostructural, and the encapsulation of a Ln ion in the ring cavity of 18-metallacrown-6 (18-MC-6) was exhibited for the first time. The structural analysis shows a ship-like 18-MC-6 core with a beset lanthanide ion connecting six ring oxygen atoms (OMC). Magnetic measurements reveal domain antiferromagnetic coupling interactions between metal ions and field-dependent slow magnetic relaxation in 1-3.

Two cobalt(ii) compounds, namely, {[Co(HL)(bpy)(H2O)2]·DMF}n (1), and {[Co(HL)(bpe)]·0.5bpe}n (2) (H3L = 1,3-bis(2-carboxylphenoxy)benzoic acid, bpy = 4,4'-bipyridine, bpe = 4,4'-vinylenedipyridine), have been synthesized using cobalt(ii) transition metal salt with phenolic carboxylic acid and different N-donor ligands. The compounds were fully characterized by elemental analysis, infrared spectroscopy (IR), single crystal X-ray diffraction analysis, and thermogravimetric analysis (TGA). Both compounds exhibit 2-D (4,4)-sql networks but with a wavelike and a double layered arrangement, respectively. Remarkably, these two compounds not only exhibit field-induced single-ion relaxation magnetization but also exceptional catalytic activities of benzylic C-H oxidation (conv. 90.3-99%; sele. 98.1-99%).

Mild crosslinking methods, which have a strong influence on biomedical hydrogels and scaffolds, have attracted wide attention in recent years. In this project, native chemical ligation (NCL) was utilized to prepare biocompatible and biodegradable hydrogels using naturally derived poly(glutamic acid) (PGA) with no additives or by-products. Firstly, thiolactone-grafted poly(glutamic acid) (PGA-HC) and cysteine-grafted poly(glutamic acid) (PGA-C) precursors were synthesized. Their structure was confirmed by nuclear magnetic resonance (NMR). Then, hydrogels crosslinked by NCL were formed by blending buffered solutions of PGA-HC and PGA-C with no additives under physiological conditions. After that, the equilibrium water content, morphology, degradation rate and mechanical properties of the hydrogels were characterized in detail. The data showed that the PGA hydrogels had gelation times, water contents and mechanical properties that were tunable by adjusting the precursor composition. Furthermore, the biocompatibility of the hydrogels was confirmed by an MTT assay. These characteristics provide a potential opportunity for the NCL hydrogels as wound dressings, skin fillings, drug delivery vehicles and tissue regeneration matrices.

Two isostructural (3,6)-connected porous coordination polymers topologically featuring both self- and interpenetration have been successfully synthesized. The porous material shows a reversible crystalline-to-amorphous transition associated with the removal and recapture of guest molecules. Particularly, the porous material demonstrates selective detection of nitrobenzene through fluorescence quenching.

Six metallacrown complexes {La(OAc)(H2O)2[15-MCCu(N)glyha-5](H2O)4}·2NO3·5H2O (1), {Gd(OAc)(H2O)[15-MCCu(N)glyha-5](H2O)3}·2NO3·5H2O (2), {Tb(OAc)(H2O)[15-MCCu(N)glyha-5](H2O)4}·2NO3·4H2O (3), {Pr(NO3)(H2O)2[15-MCCu(N)glyha-5](H2O)}·2NO3·8H2O (4), {Nd(NO3)(H2O)2[15-MCCu(N)glyha-5](H2O)2}·2NO3·7H2O (5) and {Sm(NO3)(H2O)2[15-MCCu(N)glyha-5](H2O)2}·2NO3·6H2O (6) (glyha2− = dianion glycinehydroxamic acid) have been synthesized and structurally characterized by X-ray single crystal diffraction, IR spectroscopy and elemental analysis. Spectroscopic studies show that these complexes bind to CT-DNA via an intercalative mode and cause a more B-like to a more C-like conformational change. Magnetic measurements indicate that complexes 1, 3, 4, 5 and 6 dominantly show antiferromagnetic interactions between metal centers, whereas complex 2 reveals ferromagnetic interactions.

Five organotin(IV) compounds Ph3SnL (1), (R2Sn)4O2L4 [R = n-Bu (2), n-Oct (3)], (R2Sn)4O2L2Cl2 [R = n-Bu (4), Me (5)], have been synthesized from the reactions of 2-phenyl-4-selenazole carboxylic acid (HL) with the corresponding organotin(IV) oxide or chlorides. These compounds have been characterized by elemental analysis, IR, 1H, 13C and 119Sn NMR spectroscopy, and single crystal X-ray diffraction analysis. Structural studies reveal that compound 1 exhibits a mononuclear four-coordinated tetrahedral geometry. Differently, the crystal structures of compounds 2–5 reveal the formation of the tetranuclear species containing a planar Sn4O4 core. All compounds were screened for their in vitro cytotoxic activities toward three cancer cell lines (Caco-2, A549, and HCT-116) and one normal rat hepatocyte cell line (BRL). The results indicate that both di-n-butyltin(IV) and triphenyltin(IV) derivatives not only show excellent cytotoxic activities on cisplatin-sensitive lung cancer cell line A549 and but also exhibit good cytotoxicity against cisplatin-insensitive colon cancer cell lines HCT-116 and Caco-2. Whereas, dimethyltin(IV) and di-n-octyltin(IV) complexes exhibit lower or no cytotoxic activity. The structure–activity relationship of the cytotoxicity of the title complexes has also been discussed.

A Cd(II)-based metal–organic framework, {[Cd2L(H2O)2]·DMF·H2O}n (1), has been successfully constructed from a new flexible antler-like multidentate ditopic ligand (H4L). This metal–organic framework shows highly sensitive fluorescence sensing of nitrobenzene.

Three new ZnII–ditetrazolate coordination polymers (CPs), namely [Zn(m-pdtz)(4,4′-bipy)(H2O)]n (1), [Zn2Cl2(m-pdtz)(4,4′-bipy)]n (2) and [Zn2(OH)2(m-pdtz)]n (3) (4,4′-bipy = 4,4′-bipyridine, m-H2pdtz = 5,5′-1,3-phenylene-ditetrazole), have been constructed by an in situ ditetrazolate-ligand synthesis system. The formation of m-pdtz2- ligand involves the Sharpless [2 + 3] cycloaddition reaction between isophthalonitrile (IPN) and NaN3 in the presence of Zn2+ ions as Lewis-acid catalysts under hydro/solvothermal conditions. Single-crystal structural analyses reveal that compound 1 exhibits a new 6-connected 3D structural topology constructed from dimeric {Zn2} clusters as secondary building units (SBUs), compound 2 represents a 2D sql structural feature built from rhombic tetrameric {Zn4} rings as SBUs, while compound 3 displays a new (4,6)-connected 3D structural topology constructed from rod-shaped 1D Zn-chains as SBUs. Regarding these three CPs, we have performed a thorough investigation on their crystal structure, topology, and fluorescence property.

Crystallization and decomposition of organolead trihalide perovskites (OTPs) are very sensitive to the presence of water in precursor or in ambient conditions. Thus, understanding equilibrium behaviours (crystallization and decomposition) of OTPs in aqueous solution is very critical for OTP solar cells fabricated with water-based precursor solutions. Here, equilibrium behaviours in an aqueous solution of CH3NH3PbI3 (MAPbI3) single crystals (MSCs) were studied. Diethyl ether, as an antisolvent, effectively diffused and induced MSC growth by screening different solvents (diethyl ether, tetrahydrofuran, dichloromethane, and chloroform). The structure transforms from the initial PbI2 to intermediate (HxPbI2+x·xH2O) and finally MSCs were observed by X-ray diffraction. Decomposition of MSCs in aqueous solution was significantly enhanced by potassium iodide coordination and inhibited by CH3NH3I (MAI) addition. We ascribed this inhibition behaviour to suppressing MAI migration from the MSC crystal structure. Finally, the optical properties of MSC were studied.

Eight mixed-ligand coordination compounds, [Zn(PA)(bpp)]n (1), {[Cd(PA)2(Hbpp)2(H2O)2]·2H2O}n (2), [Zn(PA)(bbi)]n (3), [Cd(PA)(bbi)(H2O)]n (4), {[Cd3(PA)2(bbi)3(Cl)2]}n (5), {[Zn6(PA)5(datrz)2(Hdatrz)2(H2O)2]·16DMF}n (6), [Cd2(PA)(datrz)2(DMF)2]n (7), and {[Cd2(PA)2(bix)2(DMF)2]·4DMF}n (8) (bpp = 1,3-bi(4-pyridyl)propane, bbi = 1,4-bis(imidazol-1-yl)butane, H2datrz = 3,5-diamino-1,2,4-triazole, bix = 1,4-bis(imidazol-1-ylmethyl)benzene), have been synthesized through the reaction of zinc and cadmium salts with pamoic acid (H2PA) and different N-donor ligands. The assembly of the ligands in different coordination modes and conformations leads to fascinating structures. 1 and 3 afford an interpenetrating polythreaded 2D → 3D motif composed of 44 sql undulated sheets, while right- and left-helices are alternatively arranged in 3. 2 possesses an interesting 3-D supramolecular network with 1-D hydrogen-bonded chains spanning different directions. 4 and 5 display both polyrotaxane and polycatenane characteristics. In 4, two 2,4-connected (4·85) nets interlocked with each other, forming a 2D → 2D polycatenating network. 5 exhibits a twofold interpenetrated (3,5,6)-connected (3·5·6)(3·52·67)(32·54·66·72·9) topology. 6 and 7 represent rare pentanodal (3,4)-connected and binodal (3,4)-connected frameworks with topologies of (4·5·6)(4·8·10)(52·6·8·9·11)(4·5·6·8·92)(4·5·7) and (4·6·8)(4·62·83), respectively. 8 displays 3-fold interpenetrated 4-connected SrAl2 topology with flexible bix ligands bridging Cd centers to form right- and left-helices. The mixed-ligand effect of the conformations of the PA ligand and N-heterocyclic coligands as well as the metal centers on the assembly of frameworks is unravelled in detail. Solid-state luminescence properties of all compounds were reported as well. Moreover, fluorescence properties of compounds 6 and 8 in various solvent suspensions at room temperature have also been investigated.

Two genuine supramolecular isomers of Cd(II) coordination polymers with an identical formula of [Cd(pptp)(ox)]n (1a and 1b) (pptp = 2-(3-(4-(pyridin-4-yl)phenyl)-1H-1,2,4-triazol-5-yl)pyridine, H2ox = oxalic acid) have been hydrothermally synthesized and characterized. Both compounds possess the rod-like binuclear [Cd2(pptp)2] subunit, which are linked by the ox ligand to afford either a flat or wavy two-dimensional (2D) 63-hcb network, depending upon whether the additive agent is used for the reaction. The photoluminescence behaviour of the compounds was also discussed.

Crystallization of a Schiff base with nickel acetate in different solvents yields a tetranuclear (dicubane-like [Ni4O4] core with two missing vertices) and a hexanuclear cluster ([Ni6O6] core with two nickel(II) ions attached to a [Ni4O4] cubane through oxygen bridges). Metal centers within these clusters exhibit ferromagnetic and antiferromagnetic coupling interactions, respectively.

Five coordination polymers with four different typological structures have been obtained based on 2,3,5,6-tetramethyl-1,4-benzenedicarboxylate acid (H2TBDC) and bipyridine ligands: 1D zigzag chain Cd(2,2′-bpy)(TBDC)(H2O)·H2O (1), 2D grid with (4,4)-net Co(H2O)2(4,4′-bpy)(TBDC)·2H2O (2), 3D interpenetrating frameworks with diamond topology Ni(4,4′-bpy)(TBDC) (3) and Cu(4,4′-bpy)(TBDC) (4), 3D porous framework with pcu network Co2(4,4′-bpy)(TBDC)2·2H2O·5DMF (5). Especially, complexes 2 and 5 with different topologies were obtained by use of the same reactant but change of the solvents. The gas sorption of complex 5 has also been studied.

A novel polynuclear Cu(I)–sulfur cluster, 1 (C54H62B30Cu6N8S6), bearing 1,2-dithiolate-o-carborane and 1,10-phenanthroline ligands was synthesized. The complex displayed rapid, low micromolar in vitro cytotoxicity against a range of epithelial tumour cells and efficient CT-DNA binding.

Solvothermal reactions of aromatic quaterphenyl-2,5,2′,5′-tetracarboxylic acid (H4qptc) ligand and transitional metal cations of MII (M = Co, Ni, Mn, Cu, Zn) in the presence of 1,10-phenanthroline (phen) afford five new coordination polymers (CPs), namely, {[M(H2qptc)(phen)(H2O)2]·2H2O}n (M = Co (1), Ni (2)), [Mn(qptc)0.5(phen)(H2O)]n (3), [Cu(qptc)0.5(phen)]n (4) and [Zn3(Hqptc)2(phen)2(H2O)2]n (5). Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric (TG) analyses. Complexes 1 and 2 are isostructures and each displays a one-dimensional (1D) zigzag chain, which further forms a 2D supramolecular architecture via inter-chain π⋯π interactions. Complex 3 possesses a (3,6)-connected CdI2 layered architecture incorporating left- and right-handed helical chains. Complex 4 exhibits a 3D porous structure with rare (3,6)-connected ant topology. Complex 5 shows a 3D (3,4,5)-connected network with (42.6)2(43.62.8)(45.64.8)2 topology. The results show that the conformations and coordination modes of H2qptc2−/qptc4− ligand are crucial factors for the formation of the different structures. Moreover, the photoluminescence of 5 has been investigated.

Three supramolecular isomeric metal–organic frameworks (MOFs) have been synthesized at different temperatures, exhibiting a structural progression from 2D (4,4) layer structures (α and β) to a 3D acentric 3-fold diamondoid network (γ).

Three dinuclear copper(I) complexes with the formula [Cu2(mu-X)2(1,2-(PiPr2)2-1,2-C2B10H10)2] (X = Cl (1), Br (2), I (3)) containing the closo carborane diphosphine ligand 1,2-(PiPr2)2-1,2-C2B10H10 have been prepared and characterized by elemental analysis, FT-IR and X-ray structure determination. The X-ray structure analyses revealed that the three complexes were isostructural and crystallized in the monoclinic system and space group C2/m. The carborane cage ligand was coordinated bidentately to the Cu(I) center through its two phosphorus atoms, and the coordination geometry around each copper atom was distorted tetrahedral. Two halogen atoms bridged the metal centers forming a dimer structure [Cu2(mu-X)2(1,2-(PiPr2)2-1,2-C2B10H10)2], which were linked into 2D supramolecular networks through novel C-H...H-B dihydrogen bonding interactions