Inorganic Chemistry Communications (v.30, #C)

Contents List (iii-xiii).

MnO2/reduced graphene oxide composite as high-performance electrode for flexible supercapacitors by Kai-Hang Ye; Zhao-Qing Liu; Chang-Wei Xu; Nan Li; Yi-Bo Chen; Yu-Zhi Su (1-4).
In this paper, we reported a facile method to prepare MnO2/reduced graphene oxide (RGO) composites and examined their applications as electrodes in flexible solid-state supercapacitors. The as-fabricated solid-state device based on these MnO2/RGO composite electrodes exhibit a good electrochemical performance with an area capacitance of 14 F cm− 2 at 2 mV s− 1 and excellent stability.In this paper, we reported a facile method to prepare MnO2/reduced graphene oxide (RGO) composites and examined their applications as electrodes in flexible solid-state supercapacitors. The as-fabricated solid-state device based on these MnO2/RGO composite electrodes exhibit a good electrochemical performance with an area capacitance of 14 F cm− 2 at 2 mV s− 1 and excellent stability.Display Omitted► MnO2/RGO composites were successfully fabricated by an electrochemical process. ► The as-prepared electrode has an excellent good electrochemical performance. ► The results indicate that the composites hold great promise for supercapacitors.
Keywords: MnO2; Reduced graphene oxide; Composites; Flexible supercapacitors;

Four new metal-organic frameworks, namely, [Zn(pimb)(hpht)]·H2O (1), Cd(pimb)0.5(hpht)(H2O) (2), [Co(pimb)(hpht)(H2O)2]·H2O (3) and [Ni(pimb)(hpht)(H2O)2]·H2O (4), (pimb = 1,4-bis(imidazol-1-yl-methyl)benzene, H2hpht = homophthalic acid) have been synthesized by using hydrothermal method based on mixed ligands of asymmetric dicarboxylate and N-donor auxiliary ligand. The networks show diverse structures and coordination modes at the metal ions. Complex 1 is a 2D corrugated network bridged by C―H···O hydrogen bond to generate a 3D framework, whereas the complex 2 features rare (3,4)-connected V2O5 topological net and stacks to give a 3D structure by C―H···π interactions. Complexes 3 and 4 are isomorphous and isostructural, where the X–H···π (X = C, O) interactions exist and stabilize the stack of their (4,4)-topological network. The factors causing structural diversities are discussed. The TGA and XPRD patterns as well as photoluminescent properties of complexes 1 and 2 are also studied in the solid state at room temperature.Four transition metal-organic frameworks based on asymmetric dicarboxylate ligand and N-donor ligand have been obtained. The architectures show diverse structures and coordination modes at the metal ions. Various non-covalent interactions play important roles in structure expansion and stabilization of title complexes. The TGA, XPRD and photoluminescent properties are studied in the solid state at room temperature.Display Omitted► Four metal complexes based on asymmetric dicarboxylate ligand were synthesized. ► Structral diversities were demonstrated. ► Non-covalent interactions were discussed. ► Photoluminescent properties were investigated.
Keywords: Asymmetric carboxylate; Imidazole-based ligand; Transition metal complex; Structural diversity; Luminescence;

Two new mixed-ligands coordination compounds Cu(Hatrz)(pda)(H2O) · H2O (1) and Cu(I)Cu(II)(atrz)(pda)(H2O) (2) (Hatrz = 3-amino-1,2,4-triazole, H2pda = pyridine-2,6-dicarboxylic acid) have been synthesized and characterized by elemental analyses, IR, XPS, single crystal X-ray diffraction and thermogravimetric analyses. Crystal structures reveal that 1 presents a zero-dimensional unit, while 2 exhibits a one-dimensional structure constructed by mixed-valence helical chain. Furthermore, the catalytic performance of compounds for the thermal decomposition of HMX (Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) was investigated by DSC.Two copper compounds based on mixed ligands with 0D and 1D mixed-valence helical chain have been synthesized and characterized. DSC analyses revealed that both compounds accelerated the thermal decomposition of HMX and compound 2 was better than 1.Display Omitted► We report two copper compounds with 0D unit and 1D mixed-valence helical chain. ► Both compounds accelerate the thermal decomposition of HMX. ► Compound 2 shows better performance on thermal decomposition of HMX than 1.
Keywords: 3-amino-1,2,4-triazole; Copper compounds; Crystal structure; HMX; Catalytic thermal decomposition;

Discrete metal complexes, [MCl2(CEAP)2] {M = Zn (1), Co (2) and Hg (3), CEAP = 4-[N,N-bis(2-cyanoethyl)amino]pyridine} and their hydrogen-bonded salts [CEAPH]2[MCl4] {M = Zn (4), Co (5) and Hg (6), CEAPH = 4-[N,N-bis(2-cyanoethyl)amino]pyridium} were prepared using CEAP or CEAP·HCl ligands and metal chlorides (molar ratio = 2:1) by both solvent-thermal synthesis method and solvent-free method. The crystal structure and powder X-ray diffraction (PXDR) studies revealed that the discrete metal complexes 13 could be converted into their hydrogen-bonded salts 46 respectively by absorbing HCl vapor in solid-gas station and these salts except for 6 could be converted back to their corresponding discrete metal complexes by grinding with KOH in solid station.The discrete complexes [MCl2(CEAP)2] {M = Zn, Co and Hg, CEAP = 4-[N,N-bis(2-cyanoethyl)amino]pyridine} and their hydrogen-bonded salts [CEAPH]2[MCl4] were prepared. The interconversions of complexes and salts were studied.Display Omitted► Solvent-free synthesis method was used to prepare the metal complex. ► The complexes have been characterized by single X-ray diffraction. ► Structural interconversions of complexes and hydrogen-bonded salts were studied.
Keywords: Solvent-free synthesis; Structural interconversion; Crystal structure; Discrete metal complex; Hydrogen-bonded salt;

A new dialdehyde (D) containing two emissive naphthalene and its [1 + 1] macrocycle with 1,2-diaminopropane were synthesized and characterized. The macrocycle was studied by 1H NMR, 13C NMR, COSY, HSQC, DEPT, mass spectrometry and microanalysis. The influence of metal cations such as Na+, K+, Cs+, Mg2 +, Ba2 +, Al3 +, Pb2 +, Cr3 +, Mn2 +, Fe3 +, Co2 +, Ni2 +, Cu2 +, Zn2 +, Cd2 +, Hg2 + and Ag+ on the photophysical properties of the macrocyclic system in DMF and DMF/H2O (9:1, v/v) mixture was investigated by means of emission spectrophotometry. The macrocycle L was found to be as an effective fluorescent sensor for Al3 + ions.A new macrocyclic chemosensor (L) containing two naphthalene fluorophores has been synthesized. Macrocycle L possesses a high affinity and selectivity for aluminum ions by enhancement of the fluorescence emission.Display Omitted► A novel fluorescent chemosensor (L) bearing two naphthalene groups was prepared. ► The macrocycle L was found to be as an effective fluorescent sensor for Al3 + ions. ► The mechanism can be described as intramolecular photoinduced electron transfer.
Keywords: Chemosensor; Naphthalene; Al3 + sensor; Macrocycle; Fluorescence;

Synthesis, structure, and catalytic activity of benzyl thorium metallocenes by Wenshan Ren; Ning Zhao; Liang Chen; Guofu Zi (26-28).
Treatment of the chloride metallocene [η 5-1,3-(Me3C)2C5H3]2ThCl2 or [η 5-1,2,4-(Me3C)3C5H2]2ThCl2 with 2 equiv of PhCH2K in diethyl ether at room temperature gives, after recrystallization from a benzene solution, the benzyl metallocenes [η 5-1,3-(Me3C)2C5H3]2Th(CH2Ph)2 (1) and [η 5-1,2,4-(Me3C)3C5H2]2Th(CH2Ph)2 (2), respectively, in good yields. Complexes 1 and 2 have been characterized by various spectroscopic techniques, elemental analyses, and X-ray diffraction analyses. They are active catalysts for the polymerization of rac-lactide, leading to the atactic polylactides with high molecular weights and narrow molecular weight distributions.Two new benzenyl thorium metallocenes have been prepared and structurally characterized. They are active catalysts for the polymerization of rac-lactide, leading to the atactic polylactides.Display Omitted► Two new benzyl thorium complexes have been reported. ► They are active catalysts for the polymerization of rac-lactide. ► They show a single-site catalyst system in polymerization of lactide.
Keywords: Thorium; Benzyl complex; Polymerization of lactide;

Synthesis, crystal structures and magnetic studies on the nickel(II) and manganese(II) complexes containing the 2-pyridyl methyl ketazine by Jing Xiang; Lin-Lin Zhao; Ya Luo; Zhong-Hua Yan; Chun-Hong Wang; Jun Zhang; Fan Zhou; Ping Mei (29-33).
Two double helical compounds with a general cationic structure [MII 2(L1 )2(Cl)3]+ have been obtained by treatment of L1 (L1  = 2-pyridyl methyl ketazine) and hydrated MIICl2 in MeOH, which were isolated as a PF6 - salt (M=Ni, 1) and a ClO4 salt (M=Mn, 2), respectively. They represent first examples of double helicates of diazine complexes containing pseudo octahedral-coordinated metal ions. Their crystal structures have been determined by X-ray crystallography and the corresponding magnetic properties have been investigated in detail.Two double helical compounds with a general cationic structure [MII 2(L1 )2(Cl)3]+ have been obtained by treatment of L1 (L1  = 2-pyridyl methyl ketazine) and hydrated MIICl2, which were isolated as a PF6 - salt (M=Ni, 1) and a ClO4 salt (M=Mn, 2), respectively. They represent first examples of double helicates of diazine complexes containing pseudo octahedral-coordinated metal ions.Display Omitted► First examples of double helicates of diazine complexes containing octahedral-coordinated metal have been obtained. ► The introduction of Cl ligand into coordination spheres of metal centers significantly varies the helical nature of L1 . ► These compounds will be useful building blocks for the construction of magnetic materials.
Keywords: Nickel(II); Manganese(II); Double helicate; Magnetic properties; Diazine ligand;

Coordination of iPr2P(O)NHP(O)iPr2 to Co(II): Simultaneous formation of octahedral and tetrahedral complexes by Nikolaos Levesanos; Alexios Grigoropoulos; Catherine P. Raptopoulou; Vassilis Psycharis; Panayotis Kyritsis (34-38).
The reaction of iPr2P(O)NHP(O)iPr2 with CoCl2  ∙ 6H2O affords simultaneously the neutral tetrahedral [Co[iPr2P(O)NHP(O)iPr2-O,O′]Cl2] and the ionic octahedral [Co[iPr2P(O)NHP(O)iPr2-O,O′]3][CoCl4] complexes. These Co(II) complexes, which are stable towards oxidation to Co(III) species, self-assemble via N-H···Cl hydrogen bonds into a “honeycomb” (6,3) network. The structural flexibility of iPr2P(O)NHP(O)iPr2 that can accommodate both tetrahedral and octahedral geometries is discussed.The reaction of iPr2P(O)NHP(O)iPr2 with CoCl2∙6H2O affords both tetrahedral [Co{iPr2P(O)NHP(O)iPr2-O,O′}Cl2] and octahedral [Co{iPr2P(O)NHP(O)iPr2-O,O′}3][CoCl4], which self-assemble into a “honeycomb” (6,3) network via N-H···Cl hydrogen bonds.Display Omitted► iPr2P(O)NHP(O)iPr2 affords tetrahedral and octahedral geometries with Co(II). ► This ligand exhibits remarkable structural flexibility. ► A (6,3) network via N-H···Cl hydrogen bonds is self-assembled.
Keywords: Cobalt; Tetraisopropylimidodiphosphinic acid; Tetrahedral and octahedral coordination; N-H···Cl hydrogen bonds; “Honeycomb” network;

The “Enders Triazole”: A well known molecule, but still a new ligand!! by Thomas Strassner; Yvonne Unger; Dirk Meyer; Oliver Molt; Ingo Münster; Gerhard Wagenblast (39-41).
1,3,4-Triphenyl-1,2,4-triazolium salts have previously been used and described in the literature as precursors for carbenes, which have been reported as organocatalysts and as neutral monodentating N-heterocyclic carbene (NHC) ligands. We now report the synthesis of 1,3,4-tri-phenyl-4,5-dihydro-1H-1,2,4-triazole-5-ylidene-platinum(II)-acetylacetonate where the triazole binds to the metal in a new coordination mode (C^C*) as an anionic bidentate ligand, where the NHC carbene interacts with the platinum center and one of the phenyl rings is cyclometalated. The complex shows phosphorescent emission in the blue region of the visible spectrum at 441 and 465 nm with a quantum yield of 42%. DFT calculations (BP86/6-31G* as well as B3LYP/6-31G*) were found to be well suited to determine the structure of the complex.The well known “Enders triazole” was previously only known as a monodentate NHC-ligand or organocatalyst. We report a new coordination mode, where the ligand binds to the metal in a bidentate fashion by cyclometalation.Display Omitted► The “Enders” triazole binds to the metal in a new coordination mode (C^C*). ► For the 1st time a triphenyl-1,2,4-triazole was cyclometalated to a Pt(II) center. ► A blue phosphorescent emission with a quantum yield of 42% was observed. ► DFT calculations are well suited to predict the structures.
Keywords: Platinum(II)-NHC-complexes; Cyclometalation; Solid-state structure; Photophysics; Phosphorescent emitter; OLEDs;

Synthesis and chemical reactivity of an Fe(III) metallacrown-6 towards N-donor Lewis bases by Manas Sutradhar; M. Fátima C. Guedes da Silva; Armando J.L. Pombeiro (42-45).
The iron(III) 18-azametallacrown-6 [Fe(ashz)(EtOH)]6 (1) (ashz3 −  = trianionic derivative of N-acetylsalicylhydrazide), prepared upon reaction of [Fe33-O)(Piv)6(H2O)3](Piv) (Piv = ButCOO) with H3ashz, reacts with N-heterocyclic Lewis bases (B = pyridine, 4-methyl pyridine, 3-amino pyridine or imidazole), leading to the stable adducts [Fe(ashz)(B)]6 (2 to 5, respectively) upon replacement of the labile ethanol ligand. All the compounds were characterized by elemental analysis, IR and ESI–mass spectroscopies and, for complexes 1 and the 3-amino pyridine adduct 4, also by X-ray crystallography. In both 1 and 4, the stereochemistry of the ligand imposes a propeller configuration of the metal cation which exhibits alternating Λ/Δ forms.Chemical reactivity of a Fe(III) 18-azametallacrown-6, [Fe(ashz)(EtOH)]6 (1) (ashz3 −  = trianionic derivative of N-acetylsalicylhydrazide), towards N-heterocyclic Lewis bases (pyridine, 4-methyl pyridine, 3-amino pyridine or imidazole) is reported. A structural comparison between the precursor 1 and the 3-amino pyridine adduct complex 4 is presented.Display Omitted► Synthesis of an iron(III) 18-azametallacrown-6, [Fe(ashz)(EtOH)]6, is reported. ► Chemical reactivity towards N-heterocyclic Lewis bases is studied. ► Labile ethanol ligands are easily replaced without affecting the metallacrown ring. ► Structural comparison between starting 18-azametallacrown-6 and an adduct is given.
Keywords: Fe(III) metallacrown-6; N-acetylsalicylhydrazide; Chemical reactivity; X-ray crystallography;

Tricarbonyl rhenium complex of 2,6-bis(8′-quinolinyl)pyridine: Synthesis, spectroscopic characterization, X-ray structure and DFT calculations by Delanie J. Losey; Blaise A. Frenzel; William M. Smith; Sean E. Hightower; Christopher G. Hamaker (46-48).
2,6-Bis(8′-quinolinyl)pyridine (bqp) reacts with pentacarbonyl rhenium chloride in toluene to give fac,fac-[Re(bqp-κ3 N)(CO)3](Cl). X-ray crystallographic data on fac,fac-[Re(bqp-κ3 N)(CO)3](Cl) show that the bqp ligand and carbonyl ligands achieve a mutually facial arrangement. A mix of MLCT and π–π* ligand centered transitions is observed for the low energy UV–vis absorption bands. The complex is emissive in solution and appears to be dominated by a MLCT-based process. Electronic and structural characteristics are supported by DFT calculations.This paper presents a combined experimental and computational study of a tricarbonyl rhenium(I) complex incorporating 2,6-bis(8′-quinolinyl)pyridine (bqp).Display Omitted► 2,6-Bis(8′-quinolinyl)pyridine (bqp) coordinated to Re is presented. ► UV–vis absorptions reveal a mix of MLCT and π–π* ligand centered transitions. ► X-ray studies show mutually facial bqp and carbonyl ligands.
Keywords: Rhenium(I) carbonyl; 2,6-Bis(8′-quinolinyl)pyridine; X-ray structure; DFT and TDDFT calculations; UV–vis spectrum;

Ruthenium(II) complexes of meso-tetrakis(4-cyanophenyl)porphyrin by Júlio S. Rebouças; Brian R. James (49-52).
A novel synthesis is presented for the meso-tetrakis(4-cyanophenyl)porphyrin complex Ru(T-pCN-PP)(CO)(H2O), the first Ru complex with this long-known porphyrin; compared to standard methods reported for other porphyrin analogues via Ru3(CO)12, extra steps involving addition of pyridine (Py) and its subsequent removal as [HPy+]Cl are required. The Py breaks down coordination polymers (as yet uncharacterized) formed via the peripheral p-cyanophenyl moiety; these materials may offer potential as porphyrin-based supramolecular solids. Removal of the CO by photolysis in MeCN solution generates Ru(T-pCN-PP)(MeCN)2, but attempts to make the bis(thiol) analogues from this precursor were unsuccessful, again due to formation of polymeric species.The illustrated Ru complexes of meso-tetrakis(4-cyanophenyl)porphyrin are described; the metallation process is lengthy and non-standard because of complications involving coordination through the peripheral p-cyano group(s). Attempted synthesis of the bis(thiol) species is unsuccessful because of related ‘polymer’ formationDisplay Omitted► First synthesis of a Ru complex containing meso-tetrakis(4-cyanophenyl)porphyrin. ► Novel synthesis of Ru(T-pCN-PP)(CO)(H2O). ► Photoloytic synthesis of Ru(T-pCN-PP)(MeCN)2 ► Likely formation of Ru–porphyrin-based supramolecular solids.
Keywords: Ruthenium; Porphyrin complexes; Cyano-porphyrins; Acetonitrile complexes;

First clathrochelate iron and cobalt(II) tris-dioximates with reactive apical substituents by Ekaterina G. Lebed; Alexander S. Belov; Alexander V. Dolganov; Anna V. Vologzhanina; Agnieszka Szebesczyk; Elzbieta Gumienna-Kontecka; Henryk Kozlowski; Yurii N. Bubnov; Igor Y. Dubey; Yan Z. Voloshin (53-57).
Direct template macrobicyclization of three 1,2-cyclohexanedione dioxime molecules with monofunctionalized HO-, H2N- and HOOC-containing phenylboronic acids on Fe2 + and Co2 + ions as a matrix afforded new macrobicyclic iron and cobalt(II) tris-dioximates with reactive apical substituents. The clathrochelates synthesized has been characterized by spectroscopic methods, X-ray crystallography and cyclic voltammetry.First iron(II) tris-dioximate clathrochelates with reactive HO-, H2N- and HOOC-terminated apical substituents were obtained by direct template condensation of 1,2-cyclohexanedion dioxime with monofunctionalized phenylboronic acids on iron and cobalt(II) ions as a matrix.Display Omitted► Iron and cobalt(II) clathrochelates with reactive apical groups were obtained. ► Template reaction gave apically functionalized iron and cobalt(II) clathrochelates. ► Terminal HO-, HOOC- and H2N-groups allow further functionalization of clathrochelates.
Keywords: Macrocyclic compounds; Clathrochelates; Iron complexes; Cobalt complexes; Ligand reactivity;

A dual shell-like heptadecanuclearity [Gd5Ni12] cluster with ferromagnetic interaction and large magnetocaloric effect by Zhong-Yi Li; Jiang Zhu; Ling Di; Yue Dai; Jian-Jun Zhang; Chun-Ying Duan (58-61).
A new dual shell-like heptadecanuclearity [Gd5Ni12(Pro)9(CMP)63-OH)92-OH)3(H2O)3] · Cl6  · 23H2O (1) cluster with proline (HPro) and N-carboxymethyl-l-proline (H2CMP) as coligands has been successfully synthesized and characterized. The compound consists of rare trigonal bipyramid {Gd5} core and triangular orthobicupola {Ni12} outer shell. The magnetic studies reveal that 1 shows ferromagnetic interactions and a large magnetocaloric effect (22.4 J kg− 1  K− 1, ΔH  = 7 T).Rare trigonal bipyramid {Gd5} core and triangular orthobicupola {Ni12} outer shell were observed in a dual shell-like heptadecanuclearity [Gd5Ni12] cluster which shows ferromagnetic coupling interactions and a large magnetocaloric effect (22.4 J kg− 1  K− 1, ΔH  = 7 T).Display Omitted► A dual shell-like heptadecanuclearity [Gd5Ni12] cluster was prepared with proline and N-carboxymethyl-L-proline as coligands through hydrothermal reaction. ► The compressed trigonal bipyramid {Gd5} core and the triangular orthobicupola {Ni12} outer shell both are rarely reported. ► The compound displays ferromagnetic interaction and a large magnetocaloric effect.
Keywords: Heptadecanuclearity; Dual shell; Coligand; Ferromagnetic interaction; Magnetocaloric effect;

The dinuclear ruthenium carbonyl cluster {Ru2(CO)623-[(Ph)C―C(H)―C(H)―N=C(H)―C(H)=C(H)(Ph)]} is produced from the reaction of cinnamaldehyde and Ru3(CO)12 in a 2.0 M solution of ammonia in ethanol. From the crystal structure it gets obvious that ammonia reacted with two molecules of cinnamaldehyde. The resulting ligand may best be described as a formally dianionic ruthenium coordinated imino-allyl-system with one exocyclic 3-phenylallylidene unit that shows no interaction with the transition metals whereas the second one is bound to ruthenium via a C―H activation step in γ-position with respect to the nitrogen atom.The dinuclear ruthenium carbonyl cluster {Ru2(CO)623-[(Ph)C―C(H)―C(H)―N=C(H)―C(H)=C(H)(Ph)]} is produced from the reaction of cinnamaldehyde and Ru3(CO)12 in a 2.0 molar solution of ammonia in ethanol. The crystal structure shows a formally dianionic ruthenium coordinated imino-allyl-system with one exocyclic 3-phenylallylidene unit whereas the second one is bound to the ruthenium carbonyl fragments.Display Omitted► A new type of ligand is formed from ammonia and two equivalents of cinnamaldehyde. ► The first carbonyl complex of a d8 metal with a non-coordinated imine moiety. ► The compound is related to catalytic reactions of imines catalysed by Ru3(CO)12.
Keywords: Ruthenium; C―H activation; Catalysis; X-ray;

The reaction of the polynucleating ligand 1,3,5-tris[bis(2-pyridylmethyl)aminomethyl]benzene (LTDPA) with Cu(ClO4)2  · 6H2O afforded the trinuclear complex [Cu3(TTDPA)(H2O)7](ClO4)6  · 5H2O (1). When the reaction was performed in the presence of the squarate dianion, C4O4 2-, the compound {[Cu6(LTDPA)21,3-C4O4)3](ClO4)6  · 12H2O}n (2) was obtained. Both compounds have been characterized by X-ray crystallography, showing a trinuclear and a 1D polymeric structures for 1 and 2, respectively. Complex 2 is composed of unusual hexametallic building blocks. Magnetic susceptibility measurements (SQUID) reveal essentially uncoupled copper(II) ions in complex 1, whereas complex 2 shows weak antiferromagnetic coupling via the squarato bridges within magnetically isolated dicopper(II) subunits of the 1D chain.An unusual hexanuclear 1D coordination polymer {[Cu6(LTDPA)21,3-C4O4)3](ClO4)6⋅ 12H2O}n (2), where TTDPA  = 1,3,5-tris[bis(2-pyridylmethyl)aminomethyl]benzene assembled from trans-bridging squarato ligands and a trinuclear building blocks [Cu3(TTDPA)(H2O)7](ClO4)6⋅ 5H2O (1) were structurally and magnetically characterized.Display Omitted► Trinuclear complex, Cu3(TTDPA)[H2O)7] (ClO4)6⋅ 5H2O (1) ► Hexanuclear 1D bridged squarato complex {[Cu6(LTDPA)21,3-C4O4)3](ClO4)6⋅ 12H2O}n (2) ► Structural and magnetic characterization of complexes 1 and 2
Keywords: Copper; Polynuclear complexes; Bridged squarate; Crystal structure; Magnetic properties;

The synthesis and X-ray structure determination of an uncommon ionic aluminum bisphenoxide [Al(THF)4(Cl)2]+[Al(mcmip)2]·1.1 THF (1) and its neutral analogue (mcmip)Al(CH2CH3)(THF) (2) are reported (mcmipH2: 2,2′-methylenebis(4-chloro-3-methyl-6-(isopropyl)phenol). The ligand was reacted in THF with diethyl aluminum chloride, respectively triethyl aluminum, under liberation of ethane to yield crystalline aluminum bisphenoxides. Compound 2 exhibits the usual structural features found in neutral THF-aluminum bisphenoxides adducts whereas the ionic compound 1 consists of a cationic octahedral aluminum dichloride moiety, [Al(THF)4(Cl)2], and an anionic di-bisphenoxide aluminate fragment [Al(mcmip)2] containing two 2,2′-methylenebis(4-chloro-3-methyl-6-(isopropyl)phenol) ligands. Both aluminum bisphenoxides were tested as catalysts in the copolymerization of cyclohexene oxide with CO2 and displayed similar good catalytic activities although the carbonate amounts present in the copolymer remain low.The synthesis and X-ray structure determination of an ionic aluminum bisphenoxide [Al(THF)4(Cl)2]+[Al(mcmip)2].1.1 THF and its neutral analogue (mcmip)Al(CH2CH3)(THF) are reported (mcmipH2: 2,2′-methylenebis(4-chloro-3-methyl-6-(isopropyl)phenol)). Both aluminum bisphenoxides were tested in the copolymerization of cyclohexene oxide with CO2 and delivered aliphatic polycarbonates in good yields with low amounts of carbonate linkages.Display Omitted► mcmipH2 = 2,2′-methylenebis(4-chloro-3-methyl-6-(isopropyl)phenol. ► New aluminum bisphenoxides using mcpipH2 as ligand. ► The new aluminium mcmip catalyse the copolymerization of cyclohexene oxide with CO2. ► Formation of aliphatic poly(ether-carbonates).
Keywords: Aluminum; X-ray structure determination; 2,2′-Methylene-bisphenoxide; Aliphatic polycarbonate;

Preparation of a MOF membrane with 3-aminopropyltriethoxysilane as covalent linker for xylene isomers separation by Zixi Kang; Jinying Ding; Lili Fan; Ming Xue; Daliang Zhang; Lianxun Gao; Shilun Qiu (74-78).
In this study, a continuous-growth Zn2(BDC)2DABCO membrane was synthesized on the NH2-terminated SAMs modified porous SiO2 substrates by using the MOF nanocrystals as seed, which was prepared by an easily scalable method with acetic acid as capping reagent. The seed crystals and membranes were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The thickness of the membranes can be varied by adjusting the repetitions of growing process. The xylene isomer mixture separation performance tests of MOF membrane were taken out.A continuous-growth MOF membrane was synthesized on the NH2-terminated SAMs modified substrates by using the MOF nanocrystals as seed, which was prepared by an easily scalable method with acetic acid as capping reagent. The xylene isomer mixture separation tests of MOF membranes were taken out.Display Omitted► The substrate was modified with SAMs to enhance the force between MOF and supporter. ► Acetic acid was added to the system as a capping reagent to compose MOF nanocrystals. ► The MOF membranes were used to the separation of xylene isomer mixtures.
Keywords: Metal organic framework; SAMs modified supporter; Nanocrystal; Xylene isomer separation;

A new 3D metal–organic coordination polymer with an unusual 3,3,8,8-connected {4.5.6}4{42.58.612.73.83}{42.59.614.7.82} topology has been synthesized under hydrothermal condition, [Cu4(BTC)2(L)(μ 3-OH)2(H2O)] · 6H2O (1) [L  = N,N′-bis(3-pyridinecarboxamide)-1,6-hexane, H3BTC = 1,3,5-benzenetricarboxylic acid], which represents the first example of metal–organic frameworks based on two types of tetranuclear copper clusters [Cu4(μ 3-OH)2(O2C-)6] and flexible bis-pyridyl-bis-amided based ligand. Moreover, the electrochemical behavior and magnetic property of 1 have been investigated.By introducing the flexible N,N′-bis(3-pyridinecarboxamide)-1,6-hexane (L) in the metal-carboxylate synthetic system, a novel 3D copper(II) complex with unusual {4.5.6}4{42.58.612.73.83} {42.59.614.7.82} topology was obtained, which represents the first example of metal–organic frameworks based on two types of tetranuclear copper(II) clusters [Cu4(μ 3-OH)2(O2C-)6] and a flexible bis-pyridyl-bis-amide based ligand. The title complex shows good electrochemical activity and dominant antiferromagnetic behavior.Display Omitted► Flexible ligand L was first introduced into the Cu-polycarboxylate system. ► A novel 3D coordination polymer 1 based on two types of Cu4 clusters is obtained. ► 1 Possesses a 3,3,8,8-connected {4.5.6}4{42.58.612.73.83}{42.59.614.7.82} topology. ► 1 Shows good electrochemical activity and dominant antiferromagnetic behavior.
Keywords: Metal–organic coordination polymer; Tetranuclear copper cluster; Flexible bis-pyridyl-bis-amide ligand; Magnetic property;

Two new complexes, [CoL2]2[Co(CH3OH)4] (1), and [Ni2L2(CH3OH)2]n (2) (H2L = 2-(((2-hydroxynaphthalen-1-yl)methylene)amino)acetic acid), have been synthesized and structurally characterized. Single-crystal X-ray analysis reveals that complex 1 is linear trinuclear mixed valence cobalt complex, while complex 2 is a 2D complex by double naphtholate bridged and synanti carboxylate bridged. Magnetic susceptibility measurements indicate that 1 shows mononuclear CoII behavior whereas 2 exhibits an antiferromagnetism behavior.Two new complexes, [CoL2]2[Co(CH3OH)4] (1), and [Ni2L2(CH3OH)2]n (2) (H2L = 2-(((2-hydroxynaphthalen-1-yl)methylene)amino)acetic acid), were successfully synthesized and magnetic properties studied.Display Omitted► A linear trunuclear cobalt 1 and a 2D nickel complex 2 have been characterized. ► The flexible ligands have two coordination modes in the complexes. ► The magnetic properties of two complexes have been investigated.
Keywords: Cobalt complex; Nickel complex; Crystal structure; Magnetic property;

Three isoreticular metal-organic frameworks based on ternary zinc(II)/triazolate/X (X = OAc, Cl) metal azolate frameworks, namely [Zn(mtz)(OAc)]·H2O (1, Hmtz = 3-methyl-1,2,4-triazole), [Zn(etz)(OAc)]·0.5H2O (2, Hetz = 3-ethyl-1,2,4-triazole) and [Zn(metz)Cl]·0.25H2O (3, Hmetz = 3-methyl-5-ethyl-1,2,4-triazole), have been synthesized by changing the substituent groups on asymmetric 1,2,4-triazolates and auxiliary anions (OAc or Cl). These frameworks have a 3-connected 4.8.10-lvt-a topological network, which can be also simplified into a 4-connected lvt net by further denoting dinuclear [Zn2(triazole)2] subunits as a square-planar 4-connected node. 1 exhibits a porous structure with 1D (d  = 3.0 Å) effective channels showing the selective adsorption behaviors of CO2 over N2, whereas 2 and 3 are nonporous structures.Three isoreticular triazolate frameworks constructed by asymmetric triazole ligands have been synthesized and characterized by X-ray diffraction, which exhibit pore size-controlled gas sorption properties.Display Omitted► Three isoreticular 1,2,4-triazolates frameworks have been synthesized. ► These structures can be viewed as 3-connected or 4-connected lvt net. ► The gas sorption properties are also investigated.
Keywords: Metal azolate framework; Triazole; lvt net; Sorption;

Under solvothermal conditions, complexes Ni(HL2) (1) and Ni(L3)·MeOH (2·MeOH) (H3L2 = N-(2-(2-hydroxybenzylideneamino)-1-(2-hydroxyphenyl)-2-(pyridin-2-yl)ethyl)picolinamide; H2L3 = 1-(pyridin-2-yl)prop-1-ene-1,2-diyl)bis(azan-1-yl-1-ylidene)bis((methan-1-yl-1-ylidene)diphenol) have been synthesized from the reaction of Ni(CH3COO)2·4H2O with 2-((pyridin-2-ylmethyleneamino)methyl)phenol (HL1) at 70 and 90 °C, respectively. The complexes were characterized by X-ray single crystal diffraction, IR spectroscopy, and elemental analysis. The plausible mechanisms for the formation of H3L2 and H2L3 via solvothermal in situ metal–ligand reactions were proposed.Two novel coordination complexes Ni(HL2) (1) and Ni(L3)·MeOH (2·MeOH) have been synthesized and characterized. The plausible mechanisms for the formation of H3L2 and H2L3 via solvothermal in situ metal–ligand reactions were proposed.Display Omitted► Two nickel(II) complexes have been prepared and characterized. ► The temperature controlled in situ metal–ligand reaction was determined. ► The plausible mechanisms for the formation of new ligands were proposed.
Keywords: Crystal structures; Nickel(II) complexes; In situ metal–ligand reaction; Carbon–carbon bond making; Carbon–oxygen bond formation;

An unprecedented mixed valence cobalt(III)/cobalt(II) ion-pair complex, [CoCO3(bipy)2]2[Co(DCA)2]⋅16H2O (1) [bipy = 2,2′-bipyridine, DCA = demethylcantharidate, exo-1,4-epoxy-cyclohexyl-2,3-dicarboxylate group, (C8H8O5)2 −], has been synthesized and characterized by elemental analysis, IR, UV–vis, Thermogravimetric analysis (TGA) and single crystal X-ray diffraction. The crystal structure of 1 consists of three independent molecular moieties: [CoCO3(bipy)2]+, [Co(DCA)2]2–, and water molecules of crystallization. Interestingly, two novel water tapes, one comprises of alternate cyclic water tetramer and octamer, the other is constructed by alternate cyclic water hexamer and carboxylate–water hybrid octamer [(H2O)2(COO)2]2 −, have been detected for the first time in the host framework of 1. The two novel water tapes are linked together by the DCA and carbonate ligands via hydrogen bonds into a 2D water layer, and then the water layers assemble complex ions ([CoCO3(bipy)2]+ and [Co(DCA)2]2 −) through hydrogen bonds, π–π interactions and electrostatic interactions to form the overall 3D metal–organic framework structure.There are nine crystal structure figures, including unit cell packing (Fig. 1), complex units (Fig. 2), two novel types of (H2O)8 clusters and water tapes containing them (Figs. 3–7), π–π interactions (Fig. 8) and 3D metal–organic framework structure of the title complex (Fig. 9). The tenth figure (Fig. 10) is the TGA and DTA curves of the title complex.Display Omitted► A mononuclear mixed valence Co(III)/Co(II) ion-pair complex has been synthesized. ► The Co(II) ions are partly oxidized to Co(III) ions during the crystallization. ► The Co(III) ions capture atmospheric CO2 to form the corresponding carbonato complex. ► The crystal water molecules form two water tapes: T4(2)8(2) and T6(0)A0-8(0)A0.
Keywords: Cobalt(III)/cobalt(II) complex; T4(2)8(2); T6(0)A0-8(0)A0; Crystal structure; Demethylcantharidate; Carbonate;

Coordination and topology versatility of metal-organic frameworks based on cadmium iodide and 5-azaarylpyrazole-3-carboxylic acids by Lu-Fang Liu; Bin Cai; Chang-Shuai He; Jian-Zhong Wu; Qian-Ming Wang; Ying Yu (105-110).
This paper studied the coordination behavior of azaarylpyrazole carboxylic acids for the first time. Hydrothermal reaction of 5-(pyridine-3-yl)pyrazole-3-carboxylic acid (H2L1) or 5-(pyrazine-2-yl)pyrazole-3-carboxylic acid (H2L2) with CdI2 afforded crystalline {[CdI(HL1)]} n (1) or {[CdI(HL2)(H2O)]·H2O} n (2), respectively. The X-ray diffraction analyses reveal that the different properties of the pyrazolecarboxylate, the iodide, and the cadmium atoms give rise to different crystal structures. The two complexes show covalently bonded two-dimensional metal-organic frameworks with different topology. The two-dimensional layers are further linked to form three-dimensional supramolecular networks through I⋯π halogen bonds or hydrogen bonds. Both complexes show luminescence enhancement compared to the corresponding ligands.In the two 2D MOFs formed by cadmium iodide and 5-(pyridine-3-yl)pyrazole-3-carboxylic acid or 5-(pyrazine-2-yl)pyrazole-3-carboxylic acid, the pyridyl and pyrazinyl substituents lead to different coordination modes of the pyrazolecarboxylate and iodine ligands, to different coordination metal sphere and topological network in the MOFs.Display Omitted► Metal ligation of azaarylpyrazole carboxylic acids was studied for the first time. ► Two 2D MOFs were obtained containing Cd, I and azaarylpyrazole carboxylates. ► Coordination behavior of the corresponding components are different. ► Ligation enhanced I⋯π halogen bond is found to exsist in one of the two MOFs. ► Both MOFs enhanced luminescence compared to the free pyrazole carboxylic acids.
Keywords: Metal-organic frameworks; Crystal structure; Luminescence; Cadmium complex; Pyrazole carboxylic acid;

Two novel zinc complexes, [Zn(H-hqc)2(bpy)(H2O)2] (1) and [Zn(H-hqc)2(bpe)]∙H2O (2), where H2-hqc = 2-hydroxyquinoline-4-carboxylic acid, bpy = 4,4′-bipyridine and bpe = 1,2-bi(4-pyridyl)ethylene, have been prepared under hydrothermal condition. Complex 1 displays a 1D rigid linear chain structure while complex 2 displays 1D flexible zig-zag chain structure. Coordination number of the central Zn ion in complex 1 is six and in complex 2 is four. The structural differences of these complexes suggest the effect of size of the bridging ligands on the construction of metal organic frameworks with the same metal ion under solvothermal conditions.Presented here are the two novel zinc complexes exhibiting auxiliary ligands controlled structural diversity.Display Omitted► Two zinc complexes based on 2-hydroxyquinoline-4-carboxylic acid were obtained. ► The complexes were structurally characterized by single-crystal X-ray diffraction. ► The complexes exhibited auxiliary ligands controlled structural diversity.
Keywords: Hydrothermal synthesis; Hydroxyquinoline carboxylate; Auxiliary ligands; Zinc; 1D coordination polymer;

Two new coordination polymers, |DMF|[Zn2(C7N2O4H6)2(C10N2H8)] (1) and |(H2O)3|[Co(C8N2O4H9)2(H2O)2] (2) have been synthesized based on 2-ethyl-1H-imidazole-4,5-dicarboxylic acid (H3EtImDC) and 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H3PrImDC) as organic ligands, respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 is a two dimensional layered structure constructed from two types of six-membered metallocycle, and the layers are stacked in an –ABCABC– sequence. For 2, the mononuclear [Co(C8N2O4H9)2(H2O)2] molecules are connected with each other through hydrogen bonds forming a three dimensional supermolecular structure. Further characterizations including elemental analyses, IR spectra, and thermogravimetric analyses have been studied.Compound 1 shows a 2D layered structure, which is generated from two types of six-membered metallocycle, and the layers are stacked in an -ABCABC- sequence. For 2, the mononuclear [Co(C8N2O4H9)2(H2O)2] molecules are connected with each other through hydrogen bonds forming a 3D supermolecular structure.Display Omitted► Both the two compounds constructed from H3ImDC derivatives with alkyl group ► Compound 1 shows a 2D structure formed by two types of six-membered metallocycle. ► Compound 2 presents a 3D supermolecular structure.
Keywords: Coordination polymer; 2-Ethyl-1H-imidazole-4,5-dicarboxylic acid; 2-Propyl-1H-imidazole-4,5-dicarboxylic acid; Layer; Supermolecular structure;

Luminescent mononuclear Pt(II) chloride complexes with C-linked 2,2′-bipyridyl tetrazole terdentate chelating ligands by Jing-Lin Chen; Xiu-Zhen Tan; Xiu-Xiu Chen; Jin-Yun Wang; Xing-Fu Cao; Li-Hua He; Jia-Yi Hua; He-Rui Wen (120-123).
Two new luminescent mononuclear Pt(II) chloride complexes possessing C-linked 2,2′-bipyridyl tetrazole terdentate chelating ligands, namely, Pt(tbpy)Cl (1) and Pt(tmbpy)Cl (2) (tbpyH = 6-(1H-tetrazol-5-yl)-2,2′-bipyridine; tmbpyH = 6-(1H-tetrazol-5-yl)-4,4′-dimethyl-2,2′-bipyridine), have been synthesized and characterized. Complex 2 adopts a distorted square-planar geometry with a mono-anionic terdentate chelate tmbpy, and it presents a zigzag head-to-tail stacking array along the a axis with alternating Pt⋯Pt separations of 3.415 and 5.469 Å. For 2, a moderately intensive broad absorption band appears at 350–425 nm in dilute DMF solution, most likely assigned as the metal-to-ligand charge transfer 1MLCT (Pt(5d) → tmbpy) transition, mixed with some halide-to-ligand charge transfer 1XLCT (Cl → tmbpy) and intraligand (IL) 1ππ* transitions inside tmbpy. It is demonstrated that the solubilities and luminescence properties of 1 and 2 are markedly influenced by the substituents in the 4 and 4′-positions of the 2,2′-bipyridyl ring. The solid-state emissions of 1 and 2 are perhaps best attributable to the 3MMLCT/3XLCT/3IL states, as supported by TD-DFT calculation of 2.Two new emissive Pt(II) chloride complexes with C-linked 2,2′-bipyridyl tetrazole terdentate chelating ligands have been synthesized and characterized. It is demonstrated that the substituents on the 2,2′-bipyridyl ring have a significant impact on the solubilities and luminescence properties of the tetrazole-based Pt(II) complexes.Display Omitted► Two new emissive Pt(II) chloride complexes Pt(tbpy)Cl (1) and Pt(tmbpy)Cl (2). ► Intermolecular Pt–Pt and π–π interactions in 2 with a mono-anionic chelate tmbpy. ► The substituents on 2,2′-bipyridyl affect the solubility and emission properties.
Keywords: Platinum(II); 2,2′-Bipyridyl tetrazole; Luminescence; Crystal structure;

Chemoselective synthesis of first representatives of bis(diorganothiophosphinyl)selenides, (R2P = S)2Se, from secondary phosphine sulfides and elemental selenium by Alexander V. Artem'ev; Ludmila A. Oparina; Nina K. Gusarova; Nikita A. Kolyvanov; Oksana V. Vysotskaya; Irina Yu. Bagryanskaya; Boris A. Trofimov (124-127).
First bis(diorganothiophosphinyl)selenides, (R2P = S)2Se, have been synthesized in 74–86% yield by the chemoselective interaction of secondary phosphine sulfides with elemental selenium (1:1 molar ratio, 100 °C, 3 h, 1,4-dioxane); the alternative bis(diorganoselenophosphinyl)sulfides, (R2P = Se)2S, are not formed under these conditions.First bis(diorganothiophosphinyl)selenides, (R2P = S)2Se, have been synthesized in 74–86% yield by the chemoselective interaction of secondary phosphine sulfides with elemental selenium (1:1 molar ratio, 100 °C, 3 h, 1,4-dioxane); the alternative bis(diorganoselenophosphinyl)sulfides, (R2P = Se)2S, are not formed under these conditions.Display Omitted► First representatives of bis(diorganothiophosphinyl)selenides were prepared. ► Reaction between secondary phosphine sulfides and selenium was investigated. ► The X-ray structures of (Cy2P=S)2Se and (Cy2P=S)2Se2 were determined.
Keywords: Phosphine sulfides; Selenium; Selenides; Crystal structure; Thioselenophosphinate;

The reactions of 2-(3-(1H-imidazol-1-yl)propyl)isoindoline-1,3-dione (L) with copper (II) chloride or copper(II) nitrate resulted in mononuclear complexes [CuL4Cl2]·12H2O (1) or [CuL4(H2O)NO3]NO3·2H2O (2) respectively; whereas the copper(II) acetate reacted with L to give a three dimensional coordination polymer {[Cu(L′)2]·4H2O}n (3), (where L′ = 2-(3-(1H-imidazol-1-yl)propylcarbamoyl)benzoate). The reaction of cadmium(II) acetate with L led to the formation of a seven-coordinated complex [CdL3(O2CCH3)2]·2H2O (4).Copper and cadmium complexes of 2-(3-(1H-imidazol-1-yl)propyl)isoindoline-1,3-dione (L) are reported. Selective copper(II) acetate promoted ring opening reaction of L leading to formation of a 3-D coordination polymer is described.Display Omitted► Complexes of 2-(3-(1H-imidazol-1-yl)propyl)isoindoline-1,3-dione (L) are reported. ► Selective formation of a 3-D copper(II) coordination polymer is described. ► Metal ion and anion selectivity in ring opening reaction is presented.
Keywords: Copper complexes; Imidazole derivative; Imide ring opening; Coordination polymer; Cadmium complex;

(H2en)0.5[BiO(OH)2(H2O)]: The first organic templated layered bismuthate by Ya-Qin Wu; Ying-Lian Qin; Cui-Rui Li; Xian-Ming Zhang (133-135).
A novel 2-D organic templated bismuth–oxygen compound (H2en)0.5[BiO(OH)2(H2O)] (1) (en = ethylenediamine) has been synthesized in the presence of ethylenediamine acting as a template under mild hydrothermal conditions. The structure was determined by single crystal X-ray diffraction and further characterized by IR spectrum, elemental analysis, scanning electron microscopy (SEM), photoluminescence and thermogravimetric analysis. In the compound, the Bi atom was coordinated by eight oxygen atoms. The BiO8 polyhedra share edges or corners with their neighbors to result in an anionic inorganic layer with protonated ethylenediamine cations occupied between layers. At ambient temperature, 1 shows a blue emission band which may be assigned to the 1P11S0 transitions of the s2 electron of the Bi3 + ion. To our knowledge, 1 is the first example of layered bismuthate templated by an organic amine.A new 2-D organic templated bismuth–oxygen compound (H2en)0.5[BiO(OH)2(H2O)] is firstly reported. The BiO8 polyhedra share edges or corners with the neighboring BiO8 polyhedra resulting in a layer and the protonated ethylenediamine molecules occupied between layers.Display Omitted► The first organic template bismuthate compound is reported. ► The Bi atom has eight-fold coordination. ► The compound displays photoluminescence property.
Keywords: Bismuthate; Organic template; Layer;

Employing piperazine (= ppz) as a bridging ligand, a new three-dimensional (3D) inorganic–organic hybrid zinc phosphite framework [Zn2(HPO3)2(ppz)]n (1) has been synthesized hydrothermally and structurally characterized by single crystal X-ray diffraction. The structure of 1 features a pillared-layer framework with unusual (3,4)-connected dmc topology. The results demonstrate that it is possible to add organic ligands into an open zinc phosphite framework for the construction of hybrid materials.Presented here is a new inorganic–organic hybrid zinc phosphite framework with unusual (3,4)-connected dmc topology.Display Omitted► A new inorganic–organic hybrid zinc phosphite framework. ► A hybrid framework material with unusual (3,4)-connected dmc topology. ► Interesting pillared-layer structure assembled from inorganic layers and organic pillars.
Keywords: Hybrid material; Solvothermal synthesis; Zinc phosphite; Crystal structure;

Cobalt induced C―H bond activation and C8-arylation of caffeine with aryl bromides by Tingting Zheng; Hongjian Sun; Faguan Lu; Klaus Harms; Xiaoyan Li (139-142).
The 8-caffeinyl cobalt(І) complex (C8-caffeinyl)Co(PMe3)4 (1) was obtained by reaction of caffeine with cobalt(I) complex CoMe(PMe3)4 via C―H bond activation with the escape of methane. The reaction of 1 with arylbromide afforded cobalt(II) complex (C8-caffeinyl)Co(PMe3)3Br (2) and the C,C-coupling products 8-aryl caffeine (3 and 4), 8-phenyl caffeine and 8-(2′-pyridinayl)caffeine. The crystal structures of complexes 1 and 2 were determined by X-ray diffraction.The 8-caffeinyl cobalt(І) complex (C8-caffeinyl)Co(PMe3)4 (1) was obtained by reaction of caffeine with cobalt(I) complex CoMe(PMe3)4 via C―H bond activation with the escape of methane. The reaction of 1 with aryl bromide afforded cobalt(II) complex (C8-caffeinyl)Co(PMe3)3Br (2) and the C,C-coupling products 3 and 4 (8-aryl caffeine).Display Omitted► Synthesis and characterization of an 8-caffeinyl cobalt(І) complex ► C―H bond activation ► C,C-coupling reaction ► Cobalt complex with trimethylphosphine as supporting ligand
Keywords: Caffeine; C,C-coupling; Cobalt; Trimethylphosphine;

Two new 3-D coordination polymers bearing linear trinuclear secondary building blocks with mixed bridging ligands, {[Ni3(tbip)2(Htbip)2(bib)2]·4H2O} n (1) and {[Co3(tbip)2(Htbip)2(btb)2]·4H2O} n (2) (H2tbip = 5-tert-butyl isophthalic acid, bib = 1,4-bis(imidazol-1-yl)butane, btb = 1,4-bis(1,2,4-triazol-1-yl)butane), were obtained and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, single-crystal X-ray crystallography and powder X-ray diffraction. Both complexes 1 and 2 display similar 3D 6-connected pcu networks containing the linear trinuclear [M3(COO)6] (M = Ni and Co) clusters as nodes.Two new coordination polymers were synthesized and characterized. Complexes 1 and 2 all display similar 3D 6-connected pcu networks containing the linear trinuclear [M3(COO)6] clusters as nodes.Display Omitted► Two 3-D complexes bearing linear trinuclear units were synthesized and characterized. ► Magnetic studies on complexes 1 and 2 are also investigated. ► The substituted groups have an effect on final structures.
Keywords: 5-tert-Butyl isophthalic acid; 1,4-Bis(imidazol-1-yl)butane; 1,4-Bis(1,2,4-triazol-1-yl)butane; Magnetic properties;

Numerous metal complexes of 1,3-bis(2-pyridylimino)isoindoline (BPI) are known, but coordination to this ligand has been limited to transition metals. Herein, we report on the synthesis of group 13 (boron, aluminum, gallium, and indium) complexes of BPI and their basic spectroscopic properties. In its deprotonated monoanionic form, the BPI ligand chelates to boron via a bidentate N^N interaction, forming a non-symmetric molecule. Coordination to aluminum, gallium, and indium occurs via a tridendate N^N^N interaction, forming a symmetric molecule. Absorption spectroscopy shows multiple absorption bands in the UV–visible region for the boron, gallium, and indium complex. A single broad absorption in the UV region was noted for the aluminum complex. Fluorescence emission spectroscopy using an excitation wavelength of 352 nm showed small differences in emission behavior among the complexes. However, with excitation at the λmax and longest λ of absorption, the aluminum complex of BPI was found to be much more emissive than the complexes of boron, gallium and indium; The latter complexes all had emission intensities on the same order of magnitude, each having a low fluorescence quantum yield.Boron, aluminum, gallium and indium complexes of 1,3-bis(2-pyridylimino)isoindoline (BPI) have been prepared. This image shows the X-ray determined structure of BPI·GaCl2 along with its absorption spectrum relative to the native BPI ligand.Display Omitted► Group 13 metal complexes of 1,3-bis(2-pyridylimino)isoindoline were synthesized. ► X-ray determined structures of boron and gallium derivatives are reported. ► B is bound to the 1,3-bis(2-pyridylimino)isoindoline ligand in a bidentate fashion. ► Al, Ga and In bind to 1,3-bis(2-pyridylimino)isoindoline in a tridentate fashion. ► UV-Vis and fluorescence emission spectra of all complexes are also reported.
Keywords: 1,3-Bis(2-pyridylimino)isoindoline; Coordination; Boron; Aluminum; Gallium; Indium;

Urothermal synthesis of two photoluminescent cadmium coordination polymers by E Yang; Hong-Yan Li; Zi-Sheng Liu; Qi-Dan Ling (152-155).
Two new Cd coordination polymers, [Cd(5-Nisp)(e-urea)]n (1), and [Cd2(5-Hisp)2(e-urea)2(en)]n (2), (where 5-Nisp = 5-nitroisophthalate; 5-Hisp = 5-hydroxyisophthalate; e-urea = ethyleneurea; en = 1,2-ethanediamine), have been urothermally synthesized by using ethyleneurea hemihydrate as the solvent. Single-crystal X-ray diffraction analyses reveal that both 1 and 2 have linear chain sub-structures linked by 5-Nisp ligands or 5-Hisp ligands into three-dimensional frameworks. The thermogravimetric behavior and the photoluminescent properties of 1 and 2 were studied.Two new 3D metal–organic frameworks with linear chain sub-structures were synthesized urothermally and structurally characterized.Display Omitted► Urothermal synthesis of a metal organic framework ► The metal organic framework with linear chain sub-structures ► The photoluminescent properties of metal organic frameworks
Keywords: Cadmium; Urothermal synthesis; Ethyleneurea; Crystal structure; Photoluminescence; Linear chain;

Hydrogen bonded water–halide {[(H2O)4X2]2 −}n tapes have been identified in the complexes [SnMe2(MePN–H)]Cl·2H2O and [SnMe2(MePN–H)]Br·2H2O where MePN is N-methylpyridoxine (PN = pyridoxine, vitamin B6). The tape can be described as planar (H2O)4 units linked by two chloride/bromide anions creating a stair-case like architecture. In the two isostructural crystals dinuclear [SnMe2(MePN–H)]2 2 + units are hydrogen bonded to the X anion of the tape via the C(5)―CH2OH fragment of the pyridoxine ligand. There is no significant interaction between the cations, which supports the organizing character of the water–halide tape.Two novel hydrogen bonded water-halide {[(H2O)4X2]2 −}n (X = Cl, Br) tapes have been identified in crystals of the complexes [SnMe2(MePN-H)]X·2H2O (X = Cl, Br) and structurally characterized.Display Omitted► Hydrogen bonded water–halide {[(H2O)4X2]2 −}n (X = Cl, Br) tapes ► Self-assembled water–halide units ► Crystal organizing ability of water–halide polymeric units
Keywords: Self-assembled water–halide units; N-methylpyridoxine; X-ray structures; Diorganotin complexes;

Stereoselective C-alkylation of an iron(II) dichloroclathrochelate via free-radical reactions with alcohols by Mikhail A. Vershinin; Alexey B. Burdukov; Natalie V. Pervukhina; Ilia V. Eltsov; Yan Z. Voloshin (159-162).
Free-radical substitution of one of the two chlorine atoms of the tris-dioximate iron(II) dichloroclathrochelate with ethanol and iso-propanol radicals proceeding with high regioselectivity at their α-carbon atoms afforded the monofunctionalized macrobicyclic products, which were characterized both in solution and in solid state by multinuclear one- and two-dimensional NMR spectroscopy and X-ray crystallography, respectively.Free-radical substitution of one of the chlorine atoms of the tris-dioximate iron(II) dichloroclathrochelate with ethanol and iso-propanol radicals proceeding with high regioselectivity afforded the monofunctionalized macrobicyclic products, which were characterized both in solution and in solid state by multinuclear one- and two-dimensional NMR spectroscopy and X-ray crystallography, respectively.Display Omitted► Iron(II) dichloroclathrochelate undergoes C-centered radical reactions with alcohols. ► C-centered radical alcohol derivatives yield C-alkylated macrobicycles. ► The reaction is first example of alkylation of a macrocyclic ligand with alcohols. ► Free-radical substitution with alcohols proceeds with high regioselectivity.
Keywords: Macrocyclic compounds; Iron complexes; Clathrochelates; Radical substitution; X-ray crystallography; NMR spectroscopy;

In this paper, two types of salicylate Cr(III) complexes [Cr(SA)2(en)]TBA·H2O (I) and [Cr(SA)(en)2]Br·H2O (II) have been synthesized (TBA = Tetrabutylammonium, SA = salicylate, en = ethylenediamine) and determined by X-ray crystallography. Then competition reaction with ethylenediamine-N,N,N′,N′-tetraacetic acid (EDTA) or apoovotransferrin (apoOTf) was monitored by UV–Visible and fluorescence spectra at 37 °C. It indicated that decomposition rate of k (I) is smaller than k (II). In the reaction with apoOTf, the releasing salicylate ligands will further be combined to OTf along with the serious fluorescence quenching of salicylate.Cr(III) can transfer from TBA[Cr(SA)2(en)] (I) or [Cr(SA)(en)2]Br to apoOTf at a different rate. The releasing salicylate ligand will further be combined to OTf along with serious fluorescence quenching of salicylate.Display Omitted► Two salicylate Cr(III)complexes [Cr(SA)2(en)]TBA and [Cr(SA)(en)2]Br were prepared. ► Their kinetics difference with apoovotransferrin were compared. ► The releasing SA is combined to OTf with serious fluorescence quenching of salicylate.
Keywords: Chromium(III); Salicylic acid; Apoovotransferrin; Kinetics; Fluorescence;

Mono- and dinuclear rhenium(I) compounds with bidentate benzimidazole chelators by Irvin N. Booysen; Muhammed B. Ismail; Orde Q. Munro (168-172).
A mononuclear rhenium(I) complex, fac-[Re(CO)3(bzch)Cl] (1), where bzch = 2-benzimidazole-4H-chromen-4-one, was isolated from the equimolar reaction between the Schiff base ligand 2-(2-aminophenyliminomethyl)-4H-chromen-4-one (H2pch) and [Re(CO)5Cl]. The 1:2 molar ratio reactions between [Re(CO)5Cl] and N-(2-hydroxybenzylidene)-benzimidazole (Hbzp) afforded a dinuclear rhenium(I) compound, (μ-bzp)2[Re(CO)3]2 (2). These new rhenium(I) compounds were characterized by NMR, UV–vis, IR, and emission spectroscopy, as well as conductance measurements and single crystal X-ray diffraction. The emission spectra for 1 in dichloromethane were well-resolved and could be deconvoluted into three main bands. The emission spectra for 2 were red-shifted by > 140 nm and markedly broadened relative to those of 1.The coordination behavior of Schiff base ligands containing chromone (H2pch, 2-(2-aminophenyliminomethyl)-4H-chromen-4-one) and benzimidazole (Hbzp, N-(2-hydroxybenzylidene)-benzimidazole) moieties towards the fac-[ReI(CO)3]+ core is explored. Novel mononuclear fac-[Re(CO)3(bzch)Cl], (1), and dinuclear μ-(bzp)2[Re(CO)3]2, (2), compounds have been isolated and characterized.Display Omitted► Novel mono- and dinuclear rhenium(I) compounds ► Schiff base ligands containing chromone and benzimidazole moieties respectively ► Three distinct emission bands ► Crystallographically-required inversion symmetry
Keywords: Rhenium(I); Benzimidazole; Bidentate; X-ray structure; Spectral characterization;

One-pot synthesis of a novel supramolecular compound based on three kinds of Keggin polyoxoanions PMo12O40 3 − with different coordination modes by Ming-li Qi; Kai Yu; Zhan-hua Su; Chun-xiao Wang; Chun-mei Wang; Bai-bin Zhou; Chun-cheng Zhu (173-177).
A novel supramolecular compound based on three kinds of Keggin polyoxoanions PMo12O40 3 − with different coordination modes [(phen)4Cu2(PMo12O40)][(phen)2Cu (PMo12O40)]2[PMo12O40][(phen)2Cu(H2O)]2·4H2O (1), has been hydrothermally prepared and characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction. Compound 1 is composed of one [(phen)4Cu2(PMo12O40)]+ cation, two [(phen)2Cu(PMo12O40)] anions, one [PMo12O40]3 − anion, two [(phen)2Cu(H2O)]2 + cations and four lattice water molecules, generating an interesting three-dimensional supramolecular framework via supramolecular interactions, in which there are three kinds of Keggin polyoxoanions PMo12O40 3 − with different coordination modes. To the best of our knowledge, the title compound represents the first example of a structure containing three kinds of Keggin POMs with different coordination modes up to now. Its electrochemical and electrocatalysis behavior have been investigated in detail.A novel supramolecular compound based on three kinds of PMo12O40 3 − with different coordination modes [(phen)4Cu2(PMo12O40)][(phen)2Cu (PMo12O40)]2[PMo12O40][(phen)2Cu(H2O)]2·4H2O (1), is reported for the first time. It proves the feasibility of the coexistence of three kinds of PMo12O40 3 − in one compound. Furthermore, 1-CPE displays good redox properties and electrocatalytic activity to reduce H2O2.Display Omitted► A new supramolecular compound based on three kinds of PMo12O40 3 − is first reported. ► 1-CPE displays unique redox property and good electrocatalytic activity. ► It provides useful prototype for design and synthesis of new compound.
Keywords: Supramolecular assembly; PMo12O40 3 −; Copper complex; Electrochemical property;

Synthesis, characterization and cytotoxicity of the Au(III) complexes with cyclic amine-based dithiocarbamate ligands by Yanan Shi; Wenhao Chu; Yuechai Wang; Shuxiang Wang; Jianlong Du; Jinchao Zhang; Shenghui Li; Guoqiang Zhou; Xinying Qin; Chenliang Zhang (178-181).
Seven new Au(III) complexes ([(PipDTC)AuCl2] (1), [(MoDTC)AuCl2] (2), [(BzoPizDTC)AuCl2] (3), [(TsPizDTC)AuCl2] (4), [(PizDTC)Au2Cl4] (5), [(MePizDTC)Au2Cl5] (6) and [(EtPizDTC)Au2Cl5] (7)) with cyclic amine-based dithiocarbamate have been synthesized, characterized and evaluated in vitro. The results indicate that these complexes exert selective cytotoxic effects against HL-60, BGC-823, Bel-7402 and KB cells lines. Complex 1 shows 11-, 5- and 1-folds higher cytotoxicity than cisplatin against KB, BGC-823 and Bel-7402 cell lines. Complex 2 exhibits higher cytotoxicity than cisplatin against BGC-823 and Bel-7402 cell lines. Complexes 3 and 4 display higher cytotoxicity than cisplatin against BGC-823 cell line. The nature of cyclic amine and the number of metal centers have important effects on cytotoxicity of these Au(III) complexes.Seven new Au(III) complexes were synthesized, characterized and evaluated. Complex 1 exhibited 5-, 11- and 1-fold higher cytotoxicity than cisplatin against BGC-823, KB and Bel-7402 cell lines.Display Omitted► Seven new Au(III) complexes were synthesized, characterized and evaluated. ► Most of the complexes exerted cytotoxicity against four cell lines with low IC50. ► Complex 1 exhibited 11-folds higher cytotoxicity than cisplatin against KB. ► The nature of cyclic-amine and number of metal centers affect on cytotoxicity. ► The corrected and annotated PDF are attached in the attachment.
Keywords: Au(III) complexes; Cyclic amine-based dithiocarbamate; Cytotoxicity;

Defect-controlled ZnO nanorod arrays for enhanced photoelectrochemical performance by Haohua Li; Youyou Fu; Haixia Liu; Maiyong Zhu; Zhen Peng; Juan Yang; Jian Li; Xinyou Huang; Yan Jiang; Qinqin Liu; Xiujiang Shi; Hui Wu; Yuehua Yang; Qiang Liu (182-186).
In this work, we demonstrated the effect of crystal defects on the photoelectrochemical properties of ZnO nanorod arrays (NRAs). Vertically aligned ZnO NRAs with different defect contents were grown on F doped SnO2 (FTO) glass substrate via facile electrochemical process and annealing treatement.The enhanced PEC performance of ZnO is attributed to the increasing light absorption and efficient charge separation and transportation which is related to the increasing donor densities.Display Omitted► The ZnO with different amount of defects were fabricated on FTO substrates. ► The enhanced PEC performance is mainly attributed to the increased donor densities. ► This work is of great significance for photocatalytic applications.
Keywords: ZnO; Nanorods; Photoelectrochemical; Defects; Anneal; Electrodeposition;