Inorganic Chemistry Communications (v.26, #C)

Contents List (iii-viii).

Solvent induced assembly of Co(II) coordination polymers with unprecedented water morphologies by Dai-yin Wang; Hua-hong Zou; Fei-long Hu; Yong-jun Li (1-6).
Three new complexes, [Co2(oba)(dbca)(H2O)2]·5(H2O) ( 1 ) [Co2(oba)(dbca)(H2O)2]·DMF(H2O) ( 2 ) and [Co6(oba)6(pyr)8]·2.5H2O ( 3 ) (H2oba = 4,4′-oxydibenzoic acid, H2dbca = diphenic acid, py = pyridine, DMF = N,N-dimethyl formamide) have been synthesized and characterized by infrared spectrum, thermal gravimetric analysis, X-ray powder diffraction and X-ray single crystal diffraction. 3D network of 1 contains interesting water clusters between the layers. Complex 2 displays similar configuration of 1 except that the free DMF molecules occupy the channel which is formed by the host. Complex 3 shows the (2,5)-connection network by using the py as the solvent. The magnetic property of complex 1 is also presented.1D water tapes were encaged in the channels in 1.Display Omitted► 1D unprecedented water clusters were observed in complex 1. ► DMF and water molecules filled in the channels of 2. ► (2,5)-connected network was observed in 3.
Keywords: Layer structure; Water cluster; Supramolecular network; Magnetic;

A novel chiral interpenetrating 3-D coordination polymer constructed by different numbers of left- and right‐handed helical chains by Jing Lu; Han-Dong Yin; Hou-Ting Liu; Su-Na Wang; Da-Cheng Li; Jian-Min Dou (7-10).
A novel coordination polymer [Co(bpbc)(H2O)2]n (1) was synthesized by hydrothermal reaction of Co(OAc)2·2H2O and 2,2′-bipyridine-4,4′-dicarboxylate acid (H2bpbc). X-ray single diffraction studies reveal that compound 1 exhibits chiral two-fold interpenetrating 3-D network, which contains different numbers of left- and right-handed helical chains. The magnetic property is also investigated.An unusual chiral interpenetrating coordination polymer is synthesized by rigid organic ligand, which contains different numbers of left- and right-handed helical chains.Display Omitted► Rigid bifunctional ligand was used to construct chiral interpenetration coordination polymer. ► This chiral coordination polymer is constructed by different numbers of left- and right‐handed helical chains. ► Antiferromagnetic coupling dominating the magnetic properties.
Keywords: Coordination polymer; Helical chain; Interpenetration; Magnetic property;

Two novel centrosymmetric dinuclear nickel(II) and zinc(II) complexes were unprecedented prepared from mono-Schiff bases with salicylaldehyde derivatives and metal acetate under solvolthermal conditions. The mono-Schiff bases bearing 2-[(3-cyclohexylaminopropylimino)methyl]phenol backbones used to prepare nickel and zinc complexes can be transformed to other ligands in the reactions, which never occur under mild synthetic procedures.Two nickel and zinc complexes were unprecedented prepared from mono-Schiff bases with salicylaldehyde derivatives and metal acetate under solvolthermal conditions. The mono-Schiff bases bearing 2-[(3-cyclohexylaminopropylimino)methyl]phenol backbones used to prepare nickel and zinc complexes can be transformed to other forms in the reactions, which never occur under mild synthetic processes.Display Omitted► Two nickel(II) and zinc(II) complexes with Schiff bases were prepared. ► The complexes have been characterized by single crystal X-ray diffraction. ► Cyclohexyl groups of Schiff bases can be removed away under solvolthermal conditions. ► The probable mechanisms were presented.
Keywords: Schiff base; Nickel complex; Zinc complex; Solvolthermal synthesis; Ligand transformation;

A new supramolecular net based on 1D chain subunits showing unprecedented 4, 4-connected tcj-4,4-Cccm topology and 3-fold interpenetration by Chang-bai Zhong; Xue-feng Feng; Xiao-zhao Tian; Yan Zhu; Gong-ming Sun; Yu-mei Song; Feng Luo (17-19).
A novel three-dimensional supramolecular framework with formulas, [Cu(H2btc)2(bpy)]n (1) was obtained by Cu(NO3)2, 4,4′-bipyridine (4,4′-bpy) and 1,3,5-benzenetricarboxylic acid (H3btc) under hydrothermal condition. Through hydrogen bonds 1 affords an unprecedented topology architecture, viz. supramolecular (4, 4)-connected net with (6.74.10)(64.7.8) tcj-4,4-Cccm topology and three-fold interpenetration.A novel three-dimensional supramolecular framework affords an unprecedented topology architecture, viz. supramolecular (4, 4)-connected net with (6.74.10)(64.7.8) tcj-4,4-Cccm topology and three-fold interpenetration.Display Omitted► A new 3D supramolecular net with three-fold interpenetration is observed. ► It presents an unprecedented (4, 4)-connected topology prototype. ► The topology is tcj-4,4-Cccm.
Keywords: (4, 4)-connected net; Hydrogen bond; Interpenetration; tcj-4,4-Cccm topology;

Carbonate-bridged tetranuclear NiII 2GdIII 2 complex generated by atmospheric CO2 fixation by Soichiro Sakamoto; Suguru Yamauchi; Hiroaki Hagiwara; Naohide Matsumoto; Yukinari Sunatsuki; Nazzareno Re (20-23).
Atmospheric CO2 fixation by a basic reaction mixture of [NiII(3-MeOsaltn)(H2O)2] and GdIII(NO3)3·6H2O gave a carbonate-bridged tetranuclear NiII 2GdIII 2 complex, (μ 4-CO3)2[NiII(3-MeOsaltn)(MeOH)GdIII(NO3)]2·H2O, where 3-MeOsaltn denotes N,N′-bis(3‐methoxy-2-oxybenzylidene)-1,3-propanediaminato. The tetranuclear structure possessing an inversion center can be described as two [NiIIGdIII] binuclear units bridged by two carbonate CO3 2 − ions: two oxygen atoms of the carbonate ion bridge the high-spin NiII and GdIII ions of a binuclear unit and the remaining oxygen atom of the carbonate ion coordinates to a GdIII ion of the adjacent binuclear unit. The temperature-dependent magnetic susceptibilities, from 1.9 to 300 K, follow the Curie–Weiss equation of χ M T  =  C  / (T  −  θ) with θ  = + 2.3 K and C  = 18.24 cm3  K mol− 1, suggesting a ferromagnetic interaction. The magnetic data were well reproduced assuming two independent [NiII–GdIII] binuclear units with the parameters of J(Ni–Gd) = + 1.2 cm− 1 and D  = + 2.1 cm− 1.Atmospheric CO2 fixation by the basic reaction mixture of [NiII(3-MeOsaltn)(H2O)2] and GdIII(NO3)·6H2O gives a carbonate-bridged tetranuclear NiII 2GdIII 2 complex, where 3-MeOsaltn denote N,N′-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato. The tetranuclear structure can be described as that two [NiII–GdIII] binuclear units are bridged by two carbonate CO3 2 − ions.Display Omitted► Atmospheric CO2 fixation is achieved by the reaction of NiII and GdIII complexes. ► The reaction gives carbonate-bridged NiII 2GdIII 2 complex. ► Two [NiIIGdIII] units are bridged by two carbonate ions to give tetranuclear structure.
Keywords: CO2 fixation; 3d–4f complex; Tetranuclear structure; Carbonate-bridge; Magnetic property;

Multi-metal prussian blue analogs may include both ferromagnetic and antiferromagnetic exchange interactions between different metal ions and exhibit the novel magnetism. We obtained a mixed ferri-ferromagnetic prussian blue analog Cu0.47Ni0.48Mn0.55[Fe(CN)6]·XH2O by chemical coprecipitation method. The compound has a typical face-centered cubic lattice and shows novel mixed ferri-ferromagnetic properties. Temperature dependence of χ − 1 curve indicates a dominant ferromagnetic coupling above 50 K. Hysteresis curves suggest the presence of long range ordering at 5 K. The decrease of the field-cooled magnetization values around 5 K is due to the anti-ferromagnetic interaction between Mn2 + and Fe3 +. Unusual magnetic properties originate from the coexistence of ferromagnetic and antiferromagnetic exchange interactions.The positive Weiss constant indicates a dominant ferromagnetic coupling above 50 K. The decrease of the field-cooled magnetization values below around 5 K is due to the anti-ferromagnetic interaction. The compound exhibits a dominant ferromagnetic coupling above 50 K and an anti-ferromagnetic one around 5 K.Display Omitted► The compound includes both ferromagnetic and antiferromagnetic exchange interactions. ► Temperature dependence of χ − 1 curve indicates a dominant ferromagnetic coupling above 50 K. ► The decrease of the field-cooled magnetization values around 5 K is due to the anti-ferromagnetic interaction. ► Unusual magnetic properties originate from the coexistence of ferromagnetic and antiferromagnetic exchange interactions.
Keywords: Unusual magnetic properties; Ferromagnetic exchange interaction; Antiferromagnetic exchange interaction;

Electrochemical synthesis of a tetrahedral trinuclear nickel(II) complex with a tridentated arenephosphinothiol ligand by Patricia Fernández-Souto; Jaime Romero; J. Arturo García-Vázquez; Antonio Sousa; Paulo Pérez-Lourido; Laura Valencia (28-30).
A trinuclear Ni(II) complex with the tridentated aromatic phosphinothiol ligand PhP(C6H4SH-2)2 has been obtained by an electrochemical procedure. The crystal structure shows that the three Ni(II) ions are in a different distorted tetrahedral environment. The denticity and flexibility of the ligand permit the tetrahedral geometry instead of the square planar geometry, the most stable geometrical state for Ni(II) d 8 systems.The reaction between a nickel plate and a tridentated arenephosphinothiol ligand following an electrochemical synthesis method, afforded a trinuclear Ni(II) complex with the three Ni(II) ions in a different distorted tetrahedral environment.Display Omitted► An arenephosphinothiol was used as ligand. ► Electrochemical synthesis has been used for the synthesis of a Ni(II) complex. ► The Ni(II) complex prepared was characterized as trinuclear.
Keywords: Nickel(II); Phosphinothiol ligand; Electrochemical synthesis; X-ray crystal structure; Trinuclear complex;

A dipodal sensor detects Al3 + in HEPES buffered THF/H2O (7:3, v/v) through excited state proton transfer, representing a quenching at 355 nm and enhancement at 480 nm. The resulting aluminium complex (1.Al 3 + ) displays a highly selective response to perchlorate anion over other anions through the emergence of a new band at 428 nm. The chemical inputs of Al3 + and ClO4 satisfies the conditions of AND molecular logic gates and in a sequential manner generates an output which mimics the functions of a security keypad lock.A dipodal sensor detects Al3 + in through excited state proton transfer. The resulting aluminium complex (1.Al3 +) displays a highly selective response to perchlorate anion. The chemical inputs of Al3 + and ClO4 satisfies the conditions of AND molecular logic gates and mimics the functions of a security keypad lock.Display Omitted► Selective detection of Al3 + through excited state proton transfer mechanism operated in a dipodal organic chemosensor. ► The resulting aluminum complex with this sensor displays a highly selective response to ClO4 anion over other anions through the emergence of a new band. ► The chemical in-puts of Al3 + and ClO4 satisfy the conditions of AND molecular logic gate and in a sequential manner generates an out-put which mimics the functions of a security keypad lock.
Keywords: Chemosensor; Recognition; Host–guest chemistry; Dipodal receptor; Al3 +;

In order to investigate the influence of flexible bis(triazole) ligands on the motifs, two zinc coordination polymers {[Zn2(bte)(btec)(H2O)4]•2H2O}n (1) and {[Zn2(btp)2(btec)]•10H2O}n (2) were synthesized by the self-assembly reaction of 1,2,4,5-benzenetetracarboxylate (btec), 1,2-bis(1,2,4-triazol-1-yl)ethane (bte), or 1,3-bis(1,2,4-triazol-1-yl)propane (btp). In 1, the bte ligands connect the 2D [Zn2(btec)]n networks to generate an unusual (3,4)-connected 3D network. The Schläfli symbol of the 3D network is (6•102)(62104). In 2, each btp ligand links two [Zn2(btec)]n 1D belts to form a (4,4)-connected 2D network with the 1D channels ca. 8.0 × 10.0 Å2 along the a-axis. The btp ligands of each 2D network interpenetrate into two adjacent identical 2D networks to form a 3D supramolecular network in 2. The luminescences and thermal stabilities of 1 and 2 were also investigated.Two zinc coordination polymers were synthesized by flexible bis(triazole) and rigid benzenetetracarboxylate co-ligands. 1 forms an unusual (3,4)-connected 3D network by each bte connects two 2D [Zn2(btec)]n networks. 2 constructs a 2D network by each btp links two [Zn2(btec)]n 1D belts.Display Omitted► Flexible bis(triazole) and rigid 1,4-benzenedicarboxylate co-ligands. ► 2D and 1D [Zn2(btec)]n. ► (3,4)-Connected 3D network. ► (4,4)-Connected 2D coordination network and 3D supramolecular network. ► The luminescences and thermal stabilities.
Keywords: Coordination polymer; (3,4)-Connected three-dimensional network; (4,4)-Connected two-dimensional network; Flexible bis(1,2,4-triazole) ligand; Benzenetetracarboxylate;

A novel luminescent 3D metal–organic framework possessing 3-fold interpenetrating (3,5)-connected net by Lian-Jie Li; Xin-Long Wang; Kui-Zhan Shao; Zhong-Min Su (42-45).
One novel metal–organic framework, namely, [Cd2(ndd)2(tib)2·H2O]n (1), [H2ndd = 2,2′-(naphthalene-1,5-diylbis(oxy))diacetic acid, tib = 1,3,5-tri(1H-imidazol-1-yl)benzene] has been prepared under hydrothermal condition and characterized by elemental analyses, infrared spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analyses. Compound 1 presents a 3D 3-fold interpenetrated (3,5)-connected network with the point symbol of (42·65·83)(42·6) topology. Furthermore, the thermal stabilities and luminescent properties of compound 1 were studied.Compound 1 presents a 3D 3-fold interpenetrated (3,5)-connected network with the point symbol of (42·65·83)(42·6) topology. Furthermore, the thermal stabilities and photoluminescent properties of compound 1 were studied.Display Omitted► Compound 1 presents a 3D 3-fold interpenetrated metal–organic framework. ► Compound 1 shows (3,5)-connected network with the point symbol (42·65·83)(42·6) topology. ► Compound 1 shows good fluorescence properties in the solid state at room temperature.
Keywords: Metal–organic framework; Hydrothermal synthesis; Crystal structure; Luminescent property;

Neutral π-stacked metallomacrocycle was prepared using fac-Re(CO)3, and linear ditopic π-conjugated nitrogen donors in water–toluene mixture under reflux condition. Two ethylene units in the cycle are parallel to each other with a distance of 3.4 Å, which undergo topochemical conformational change from a parallel conformation to criss-cross conformation and photoreduction under UV-light irradiation through single-crystal-to-single-crystal transformation (SCSC). The π-stacked cycle and its photoproducts were characterized by 1H NMR spectroscopy and X-ray diffraction studies.Neutral π-stacked metallomacrocycle was prepared. Ethylene units in metallacycle undergo topochemical conformational change from parallel conformation to criss-cross conformation and photoreduction under UV-light irradiation through single-crystal-to-single-crystal transformation.Display Omitted► Neutral π-stacked metallomacrocycle ► Metallacycle to metallacycle via single-crystal-to-single-crystal transformation. ► Topochemical conformation change and reduction via SCSC under light. ► Transformation of C=C bonds from a parallel to criss-cross conformation in the cycle.
Keywords: Metallomacrocycle; Photochemistry; Rhenium; Single-crystal-to-single-crystal; Topochemistry;

Two isostructural lanthanide complexes, [Ln (dbtec)0.5(ox)0.5·3H2O]n, [Ln = Dy (1), Yb (2)] (H4dbtec = 3,6-dibromobenzene-1,2,4,5-tetracarboxylic acid; H2ox = oxalic acid), have been synthesized under the hydrothermal method and characterized by single-crystal X-ray diffraction, X-ray powder diffraction (PXRD), thermogravimetric analysis (TGA) and elemental analysis (EA) and IR spectra. Complex 1 and 2 present a 2-nodal (4,6)-connected 3D fsc network. The 13C NMR of H4dbtec indicates ox in 1 and 2 is generated by the in situ decomposition of H4dbtec. Additionally, the photoluminescent properties of 1 and 2 are also discussed.Two isostructural lanthanide complexes, [Ln (dbtec)0.5(ox)0.5·3H2O]n, [Ln = Dy (1), Yb (2)] (H4dbtec = 3,6-dibromobenzene-1,2,4,5-tetracarboxylic acid; H2ox = oxalic acid), have been synthesized under the hydrothermal method and characterized. In 1 and 2 oxalic acid (in situ reaction generated) plays an important role in determining the 3D frameworks. The thermal stability and luminescent behavior of 1 and 2 were also discussed.Display Omitted► Two novel 3D Ln(III) coordination polymers were synthesized and characterized. ► In situ oxalic acid generated during the hydrothermal reaction of H4dbtec. ► The photoluminescent properties of 1 and 2 are also discussed.
Keywords: Crystal structure; Lanthanide; Luminescence; fsc network; In situ reaction;

Two new magnetic entities, [Cu(atr)(μ-OH)(NO3)] n (1) and {[Cu(atr)2(NO3)]·NO3} n (2) (atr = 4-amino-1,2,4-triazole), were respectively obtained by tuning the molar ratio of initial reactants and structure-directing agent. Complex 1 exhibits a grid-like coplanar layer with hydroxyl group bridged linear ―CuOCu― chains interlinked by pairs of exotridentate μ 3-atr ligands. Instead, 2 displays a linear chain periodically extended by two μ-atr and one nitrate connectors. The structural transformation is significantly governed by the switchable coordination of exocyclic amino group of atr ligand. Antiferromagnetic interactions with variable strength between the nearest intra-chain spin carriers lead to overall S  = 0 spin ground states of the two complexes.Two magnetic entities with 2D coplanar layer and 1D linear chain were generated by varying molar ratios of initial reactants and structure-directing agents, exhibiting different antiferromagnetic couplings to an overall S  = 0 spin ground states.Display Omitted► Two complexes, a coplanar 2D layer and a 1D linear chain, were obtained. ► The structures are governed by the exocyclic amino group of atr ligand. ► Magnetic couplings are well associated with the obtained structural parameters.
Keywords: Coordination polymers; 4-Amino-1,2,4-triazole; Magnetism; Crystal structure; Switchable coordination;

Two heteronuclear 3d–4f complexes obtained by salen-type ligand N,N′-bis(2-hydroxy-3-methoxybenzylidene)-1,3-diaminopropane (H2L1) and N,N′-bis(2-hydroxy-3-methoxy benzylidene)-1,2-diaminohexane (H2L2) have been isolated. They are co-crystallized complex [Yb(ZnL1)(OAc)2(H2O)]·[Yb(ZnL1)(OAc)3]·PF6·CH3OH (1), trinuclear complex [Sm(ZnL2)2Cl2(H2O)2]·PF6 (2). In complexes 1 and 2 the anion PF6 called counteranion is not only a role to neutralize overall charge in the solid but also to regulate frameworks. The complexes were structurally characterized by single crystal X-ray crystallographic studies and their photophysical properties were investigated.Two salen-type heteronuclear 3d–4f complexes were isolated and structurally characterized by single crystal X-ray crystallographic studies. In the two complexes, the anion PF6 called a counteranion has the roles of neutralizing the overall charge in a solid and regulating frameworks. Their photophysical properties were also investigated.Display Omitted► Heterometallic complexes Zn–Ln (Ln = Yb, Sm) assembled from salen-type ligand ► The polynuclear structure engineering by framework-regulator PF6 anions ► Enhancement of near-infrared and luminescent properties
Keywords: Salen-type; Heteronuclear 3d–4f complex; Counteranion; NIR; Luminescence;

Solvent-free direct cyclopalladation of sulfides on silica gel by Jonathan E. Kukowski; Jessica R. Lamb; Valeria A. Stepanova; Irina P. Smoliakova (64-65).
Direct cyclopalladation of benzyl methyl sulfide, benzyl phenyl sulfide and 1,3-bis(methylthiomethyl)benzene using Pd(OAc)2 can be accomplished using silica gel instead of a solvent. The yields of the corresponding cyclopalladated complexes in these green transformations are very similar to those obtained using conventional solvent conditions. The X-ray crystallographic data for trans-Pd(HL)2Cl2 (HL = benzyl methyl sulfide) are reported.Solvent‐free cyclopalladation of sulfides with Pd(OAc)2 on SiO2 can be accomplished with the yields similar to those reported for the reactions in solvents.Display Omitted► Direct cyclopalladation of sulfides on SiO2 is described. ► Yields of complexes obtained on SiO2 are similar to those prepared using solvents. ► The molecular structure of trans-Pd(HL)2Cl2 (HL = benzyl methyl sulfide) is reported.
Keywords: C,S-palladacycle; S,C,S-palladacycle; Reactions on silica gel; Cyclopalladation of sulfides;

The ionic nature of methylsulfur trichloride species by Lucas S. Rodríguez Pirani; Mauricio F. Erben; Carlos O. Della Védova (66-68).
The Raman spectrum of the methyldichloro-sulfonium(IV) chloride, CH3SCl2 +Cl, is reported. The unambiguous vibrational assignment for the CH3SCl2 + cation is made on the basis of the solid state Raman spectra aided by high-level quantum chemical calculations and a normal mode analysis. Actually, the former reported methylsulfur trichloride, CH3SCl3, can be now described as CH3SCl2 +Cl.The analysis of both Raman spectrum and results from the quantum chemical calculations suggests a CH3SCl+ Cl ionic structure for methyldichloro-sulphonium(IV) chloride.Display Omitted
Keywords: Sulfonium salts; Raman spectroscopy; Methyldichloro-sulfonium chloride; Ionic/covalent;

Rapid synthesis of Group VI carbonyl complexes by coupling borohydride catalysis and microwave heating by Kurt R. Birdwhistell; Brian E. Schulz; Paula M. Dizon (69-71).
Several Group VI tetracarbonyl phosphine and tertiary amine complexes [M(CO)4  L2, M = Cr, Mo, W, L2  = 2PPh3, dppm, dppe, dppp, dppb, bpy, phen, dppf] were synthesized in minutes in the microwave at moderate temperature, atmospheric pressure, and utilizing NaBH4 as a catalyst. The reactions were optimized by careful solvent selection. The octahedral complexes were isolated in percent yields ranging from 17 to 95. The lower temperatures, shorter reaction times, benign solvents, and lower pressures as compared to the traditional thermal syntheses provide a rapid, eco-friendly synthetic route to these common Group VI complexes.Display Omitted► Rapid synthesis of Group VI metal carbonyl derivatives; ► Use of borohydride catalysis for metal carbonyl syntheses; ► Microwave assisted synthesis; ► cis-Selectivity observed; ► Benign alcohol solvents used in the synthesis of metal carbonyl complexes.
Keywords: Group VI tetracarbonyl complexes; Rapid synthesis; Microwave; Catalysis; Sodium borohydride; cis-Selectivity;

ReVN and TcVN complexes with a novel tetradentate hybrid benzamidine/thiosemicarbazone ligand by Hung Huy Nguyen; Juan Daniel Castillo Gomez; Ulrich Abram (72-76).
N-(diethylthiocarbamoyl)benzimidoyl chloride reacts with o-aminoacetophenone 4-methylthiosemicarbazone under formation of a novel N2S2 benzamidine/thiosemicarbazone ligand (H2L). The reaction of H2L with [ReNCl2(PPh3)2] yields a red complex of the composition [ReN(L)]. The molecular structure of [ReN(L)] reveals a square-pyramidal environment around the Re atom, in which the organic ligand occupies all four positions of the equatorial plane. The reaction of H2L with [TcNCl2(PPh3)2] results in a mixture of [TcN(L)] and a side-product of the composition [TcN(PPh3){Et2NC(S)NH}(L′)] (L′ = 1,10b-dimethyl-5-phenyl-1,10b-dihydro-[1,2,4]triazolo[1,5-c]quinazoline-2-thiolate). The formation of diethylthiourea and HL′ is the result of a metal-driven decomposition of H2L followed by cyclization.The novel N2S2 benzamidine/thiosemicarbazone hybrid ligand H2L reacts with [TcNCl2(PPh3)2] under formation of a mixture of [TcN(L)] and a side-product containing two fragments of H2L, while with the analogous rhenium precursor [ReN(L)] is formed exclusively.Display Omitted► A tetradentate benzamidine/thiosemisemicarbazone hybride ligand has been prepared. ► The novel ligand forms stable [MN(L)] complexes (M = Re, Tc). ► A metal-driven decomposition of H2L is observed with [TcNCl2(PPh3)2]. ► The decomposition fragments of H2L coordinate to Tc.
Keywords: Rhenium; Technetium; Thiourea derivatives; Thiosemicarbazones; Cyclization; X-ray structure;

With a new pentacyanidecobalt(III) precursor K2[Co(CN)5(CH3CN)] and a bicompartimental Schiff base manganese(III) compound, a new two-dimensional cyanide-bridged Co(III)-Mn(III) coordination polymer constructed by hydrogen-bond interactions has been successfully synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single X-ray diffraction analysis reveals this cationic cyanide-bridged tetranuclear complex is self-complementary through coordinated aqua ligands from one complex and the free O4 compartments from the neighboring complex, giving interesting 2D supramolecular structure. Investigation over magnetic susceptibility reveals the overall weak antiferromagnetic coupling between the adjacent Mn(III) ions.With a new pentacyanidecobalt(III) precursor K2[Co(CN)5(CH3CN)] and a bicompartimental Schiff base manganese(III) compound, a new two-dimensional cyanide-bridged Co(III)-Mn(III) coordination polymer constructed by hydrogen-bond interactions has been successfully synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single X-ray diffraction analysis reveals this cationic cyanide-bridged tetranuclear complex is self-complementary through coordinated aqua ligands from one complex and the free O4 compartments from the neighboring complex, giving interesting 2D supramolecular structure. Investigation over magnetic susceptibility reveals the overall weak antiferromagnetic coupling between the adjacent Mn(III) ions.Display Omitted► New cyanide precursor and bicompartimental Schiff base manganese(III) compound used to assemble heterometallic complex. ► Interesting 2D supermolecular structure constructed by intermolecular hydrogen bond interactions. ► Magnetic properties of the complex are investigated.
Keywords: Cyanide-bridged; Synthesis; Crystal structure; Magnetic properties;