Substituent Dependent Dimensionality in Luminescent Zinc Isophthalate Coordination Polymers Containing Bis(3‐pyridylmethyl)piperazine

Divalent zinc coordination polymers containing bis(3‐pyridylmethyl)piperazine (3‐bpmp) and isophthalate ligands have been hydrothermally synthesized and structurally characterized by single‐crystal X‐ray diffraction. {[Zn(ip)(H3‐bpmp)]ClO₄·4H₂O}_n ( 1 , ip = isophthalate) has twofold parallel interpenetrated (4,4) grid cationic coordination polymer nets, with unligated perchlorate ions and intriguing infinite water molecule chains. {[Zn₂(NO₂ip)₃(H₂3‐bpmp)(H₂O)₅]·3H₂O}_n ( 2 , NO₂ip = 5‐nitroisophthalate) exhibits a supramolecular lattice built from 1D chain motifs, revealing a significant dependence of topology on the steric bulk of the dicarboxylate ligand. Luminescent properties for 1 and 2 are also reported.     

Divalent Metal 2,5‐Thiophenedicarboxylate Coordination Polymers with the Conformationally Flexible Bis(4‐pyridyl­formyl)homopiperazine Ligand

Divalent metal coordination polymers containing the rigid 2,5‐thiophenedicarboxylate (tdc) ligand and the conformationally flexible dipyridylamide ligand bis(4‐pyridylformyl)homopiperazine (bpfh) show different layer topologies and chirality. As determined by single‐crystal X‐ray diffraction, {[Cd(tdc)(bpfh)(H₂O)] · 3H₂O}_n ( 1 ) shows a twofold parallel interpenetrated centrosymmetric (4,4) layered grid structure. {[Zn(tdc)(bpfh)] · H₂O}_n ( 2 ) exhibits a similar system of twofold interpenetrated (4,4) grid‐like layers, but in contrast to 1 , it crystallizes in an acentric space group. {[Ni₂(tdc)₂(bpfh)₂(H₂O)] · 2H₂O}_n ( 3 ) possesses {Ni₂(μ‐H₂O)(OCO)₂} dimeric units connected into a doubled layer motif by the full span of the tdc and bpfh ligands. Weak antiferromagnetic coupling is observed within the dimeric units in 3 [g = 2.172(6) and J = –0.79(1) cm^–1]. Compounds 1 and 2 undergo blue‐violet fluorescence upon ultraviolet irradiation; the cadmium derivative 1 shows potential as a sensor for the solution‐phase detection of nitrobenzene although coordination polymer exfoliation likely occurs. Thermal decomposition behavior of the three new phases is also discussed.     

Multi‐dimensional Copper(II) Coordination Polymers via Self‐assembly Induced by Sodium Ions

Two novel copper(II) coordination polymers, [CuNa₂(Hnta)₂]_n ( 1 ) and {[CuNa₂(pht)₂(H₂O)]·H₂O}_n ( 2 ) (H₃nta = nitrilotriacetate acid, H₂pht = o‐phthalic acid), have been synthesized and characterized.The sodium ions play an important role in the formation of the multi‐dimensional structures. The X‐ray structure of [CuNa₂(Hnta)₂]_n ( 1 ) is three‐dimensionally cross‐linked with building blocks [Cu(Hnta)₂]^2—connected by three sodium ions. The structure of {[CuNa₂(pht)₂(H₂O)]·H₂O}_n ( 2 ) can be described as pht units connected by Na ions via Na—O bonds to form chains, which are linked by Cu^II ions to make a 2D network. The IR spectra and thermal properties are also reported.     

Syntheses,Structures, and Catalytic Properties of Three Copper(II) Coordination Polymers Based on 2,3,5,6‐Tetrafluoro‐1,4‐bis(triazole‐ylmethyl)benzene and Benzene Carboxylate Ligands

Three new mixed‐ligand coordination polymers of Cu^II, namely, [Cu(Fbtx)(L1)(H₂O)]_n ( 1 ), [Cu(Fbtx)_0.5(HL2)(H₂O)₂]_n ( 2 ), and {[Cu(Fbtx)_1.5(HL3)(H₂O)] · H₂O}_n ( 3 ) [Fbtx = 2,3,5,6‐tetrafluoro‐1,4‐bis(1,2,4‐triazole‐1‐ylmethyl)benenze, H₂L1 = terephthalic acid, H₃L2 = trimesic acid, NaH₂L3 = 5‐sulfoisophthalic acid monosodium salt], were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectra, and single‐crystal and powder X‐ray diffraction techniques. All the complexes have a two‐dimensional (2D) coordination layer structure. Of these, 1 displays a planar 4⁴‐ sql structure whereas both 2 and 3 are highly undulated 6³‐ hcb nets. Moreover, their thermal stability and catalytic behaviors in the aerobic oxidation of 4‐methoxybenzyl alcohol were also investigated as well. The results indicate that the benzene dicarboxylate ligands have an effective influence on the structures and catalytic properties of the resulting coordination polymers.     

Metal‐ and Substituent‐Dependent Structural Diversity in ­Cobalt and Nickel Isophthalate Coordination Polymers with Bis(4‐pyridylformyl)piperazine Tethers

Hydrothermal reactions of nickel or cobalt nitrate with the dipyridylamide ligand bis(4‐pyridylformyl)piperazine (4‐bpfp) and either 5‐methoxyisophthalate (H₂omeip) or 5‐methylisophthalate (H₂mip) afforded a series of coordination polymers that were structurally characterized by single‐crystal X‐ray diffraction. Different synthetic conditions afforded the 1D chain phase {[Ni(Homeip)₂(H₂omeip)(bpfp)] · 2H₂O}_n ( 1 ) or the mutually inclined interpenetrated (4, 4) grid system in {[Ni(omeip)(bpfp)(H₂O)] · 2H₂O}_n ( 2 ). The analogous cobalt phase {[Co(omeip)(bpfp)] · 3H₂O}_n ( 3 ) lacks bound water molecules, which enforces a non‐interpenetrated (4, 4) grid structure based on {Co₂(OCO)₂} dinuclear clusters. Similar clusters are seen in {[Co(mip)(bpfp)(H₂O)₂] · 3.5H₂O}_n ( 4 ), which manifests a 1D ribbon structural motif. Its nickel congener {[Ni(Hmip)₂(bpfp)(H₂O)₂] · 2H₂mip}_n ( 5 ) also shows a 1D chain motif. A variable temperature magnetic susceptibility study indicates antiferromagnetic coupling within the dimeric units in 3 and 4 concomitant with single ion effects. Additionally, thermal degradation properties of these new materials are described.     

Divalent Nickel and Monovalent Copper Pseudohalide Coordination Polymers Incorporating the Kinked Organodiimine 4,4′‐Dipyridylamine: From a (4,4)‐Type Lamellar Motif to an Unprecedented Staircase Morphology

The divalent nickel isothiocyanate coordination polymer [Ni(NCS)₂(dpa)₂] ( 1 ) has been prepared in high yield via the hydrothermal combination of Ni(SCN)₂ with the kinked tethering ligand 4,4′‐dipyridylamine (dpa), and characterized via single crystal X‐ray diffraction, infrared spectroscopy and elemental and thermal analysis. 1 manifests offset stacked 2‐D (4,4)‐topology layered motifs organized into 3‐D via interlamellar supramolecular N–H···S hydrogen bonding. Hydrothermal reaction of CuCl₂·2H₂O, NaSCN, and dpa afforded the copper (I) thiocyanate coordination polymer [Cu₂(SCN)₂(dpa)] ( 2 ), whose single crystal structure revealed unprecedented 1‐D [Cu₂(SCN)₂] zig‐zag staircase motifs constructed via connection of the Cu₂S₂ “stair steps” at their adjacent sides via μ₃‐1,1,3‐SCN anions. The 3‐D structure of 2 is propagated by covalent linkage of each [Cu₂(SCN)₂] staircase to four others through dipodal dpa tethering ligands, enhanced by N–H···S and C–H···S supramolecular interactions to two other staircases.     

Two Novel 3D Copper Phthalate Coordination Complexes Incorporating Isomeric Flexible Bis(pyridylformyl)piperazine Ligands

Two novel metal‐organic coordination complexes [Cu(3‐bpfp)(pht)(H₂O)] · 2H₂O ( 1 ) and [Cu₃(4‐bpfp)(pht)₂(OH)₂] · 2H₂O ( 2 ) were hydrothermally synthesized by self‐assembly of phthalic acid (H₂pht), flexible bis(pyridylformyl)piperazine ligands [3‐bpfp = bis(3‐pyridylformyl)piperazine, 4‐bpfp = bis(4‐pyridylformyl)piperazine], and copper chloride. Single crystal X‐ray diffraction analysis revealed that the adjacent Cu^II ions are connected by pht showing different coordination modes [a bis(monodentate) coordination mode for 1 and a monodentate‐bidentate coordination mode for 2 ] to form 1D Cu‐pht‐Cu chains in 1 and 2D Cu‐pht layers in 2 . In compound 1 , a twofold interpenetrated CdSO₄‐like topology is formed by connection of 3‐bpfp. Using the isomeric ligand 4‐bpfp instead of 3‐bpfp resulted in the formation of 2 , which displays a novel 3, 4, 4, 4‐connected tetranodal 3D coordination polymeric framework. The ligand 3‐bpfp adopts a μ₂‐bridging coordination mode in 1 (by ligation of the pyridyl nitrogen atoms), whereas the ligand 4‐bpfp adopts a μ₄‐bridging coordination mode (by ligation of pyridyl nitrogen and carbonyl oxygen atoms) in 2 . Moreover, the electrochemical properties of carbon paste electrodes bulk modified with the two copper complexes were studied.     

Nitroaromatic‐detecting Layered Cadmium Cyclohexyldicarboxylate Coordination Polymers with Long‐Spanning Dipyridyl Pillaring Ligands

Three new divalent cadmium coordination polymers containing cyclohexyldicarboxylate and pillaring dipyridylamide ligands have been prepared and structurally characterized via single‐crystal X‐ray diffraction. All three compounds exhibited layered structures, but with different topologies and interpenetration schemes. [Cd₂(12chedc)₂(ebin)(H₂O)₂]_n ( 1 ) [12chedc = 1,2‐cyclohex‐4‐ene‐dicarboxylate, ebin = ethylenediamine(bis)isonicotinamide] displays a 2D 3,4‐connected net with (4²6)(4²6³8) topology, also known as the V₂O₅ structural type. {[Cd(13cdc)(ebin)] · H₂O}_n ( 2 ) (13cdc = cis‐1,3‐cyclohexanedicarboxylate) showed a rare 2D + 2D → 3D parallel polycatenated system of looped layer networks. {[Cd(13cdc)(hbn)] · H₂O}_n ( 3 ) [hbn = hexanediamine(bis)nicotinamide] manifests a (4²6)(4²6⁷8) network, also known as the 3,5L2 net. All three materials were assayed as fluorescent “turn‐off” sensors for the detection of nitrobenzene in solution. Thermal decomposition behavior of the new phases is also discussed.     

Die Kristallstrukturen von (NBu4)[(Ph3Sn)3(MoO4)2] und (NBu4)[(Ph3Sn)3(MoO4)2]·CH3CN: Organozinnmolybdate mit neuartigen 3D‐Netzwerken

The Crystal Structures of (NBu₄)[(Ph₃Sn)₃(MoO₄)₂] and (NBu₄)[(Ph₃Sn)₃(MoO₄)₂]·CH₃CN: Organotin Molybdates with Novel 3D Networks The reaction of (NBu₄)₂[Mo₆O₁₉] with Ph₃SnCl and NBu₄OH in acetonitrile as solvent leads to the formation of (NBu₄)[(Ph₃Sn)₃(MoO₄)₂] ( 5 ). 5 and (NBu₄)[(Ph₃Sn)₃(MoO₄)₂]· CH₃CN 6 have been characterized by single crystal structure analysis at 220 K. 5 crystallizes monoclinic with a = 1429.5(4) pm, b = 2292.2(3) pm, c = 2269.7(5) pm, β = 107.42(3)°, space group Cc, 6 crystallizes orthorhombic with a = 1820.5(1) pm, b = 1848.6(2) pm and c = 2143.9(1) pm, space group P2₁2₁2₁. The crystal structures of 5 and 6 consist of isolated (NBu₄)⁺ cations and anionic 3D networks of Ph₃SnO₂ trigonal bipyramides and MoO₄ tetrahedra which are linked by common oxygen atoms.     

Synthesis,Crystal Structures,and Luminescent Properties of Two Complexes based on 5‐tert‐Butylisophthalic Acid and 1, 2‐Bis(4‐pyridyl) Ethane

Abstract. Two coordination polymers, namely, [Zn(bpe)_0.5(Htbip)(tbip)_0.5] · H₂O ( 1 ) and [Cd(bpe)_0.5(tbip)] ( 2 ) [H₂tbip = 5‐tert‐butylisophthalic acid and bpe = 1, 2‐ bis(4‐pyridyl) ethane] were synthesized through hydrothermal reactions. Single‐crystal X‐ray diffraction analysis reveals that complex 1 presents a three‐dimensional (3D) six‐connected uninodal structure with the type of topology of svi‐x/I4/mcm → Ibam, whereas complex 2 holds a 2D 4⁴‐sql layer structure. Moreover, the photoluminescent properties of the complexes at room temperature were investigated.     

Synthesis and Luminescent Properties of Two Zinc(II) Coordination Polymers Constructed by 4‐(Pyridin‐4‐ylmethoxy)benzolic Acid Ligand

Two coordination polymers, namely [Zn(L)Cl] ( 1 ) and [Zn(L)₂] ( 2 ) [L = 4‐(pyridin‐4‐ylmethoxy)benzolic acid] were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction analyses, powder X‐ray diffraction, and thermogravimetric analysis. Compounds 1 and 2 have a two‐dimensional square‐shaped structure (the dimensions are 15.43 × 15.43 Å for 1 and 12.064 × 15.017 Å for 2 ) with (4⁴ · 6²) topology. Moreover, compounds 1 and 2 exhibit a 3D supramolecular structure made up by strong π–π interactions from the adjacent layers. Furthermore, compounds 1 and 2 show good fluorescence properties in the solid state at room temperature.     

Study of the Interaction of Bis(4‐pyridylthio)methane with Copper(II) Chloride and Bromide

The new ligand bis(4‐pyridylthio)methane (4‐bpytm) ( 1 ) and its complexes [CuX₂(4‐bpytm)] and [CuX₂(4‐bpytm)₂] (X = Cl and Br) ( 2 – 5 ) have been prepared and characterized by elemental analysis, IR‐Raman, UV/Vis spectroscopy. The structures of (4‐bpytm) ( 1 ), [CuCl₂(4‐bpytm)₂] ( 3 ) and [CuBr₂(4‐bpytm)₂] ( 4 ) were determined by single‐crystal X‐ray diffraction analysis. X‐ray analysis of the 1:2 derivatives reveals that the copper atom has a distorted (4 + 2) octahedral environment. The copper atom is coordinated by four nitrogen atoms from four bridging 4‐bpytm ligands and two halogen atoms. The axial Cu–N bonds are considerably longer than the equatorial Cu–N bonds owing to JahñTeller distortion. CuX₂ units are linked to each other through bridging 4‐bpytm ligands to form a 2D interpenetrated coordination polymer. The structural parameters of the 4‐bpytm ligand in these complexes were compared with those of the free ligand.     

Coordination of Deprotonated Saccharin in Copper(II) Complexes. Structural Role of the Saccharinate Directed by the Ancillary N‐heterocyclic Ligands

Four different coordination patterns were observed following the partial or complete thermodynamically‐controlled ligand substitution of the hydrated tetraaquabis(o‐sulfobenzimidato‐N)copper(II) complex with heterocyclic bases as examined by X‐ray diffraction. The N‐heterocycle directs the o‐sulfobenzimidate (saccharinate) anion into the immediate coordination polyhedron of the metal by any of the imido, carbonyl or sulfonyl functionalities, or as a lattice counter‐ion in the crystal lattice. Aqua(o‐sulfobenzimidato‐O)tetrakis(4‐methylpyridine)copper(II) o‐sulfobenzimidate hemihydrate ( 1 ) crystallizes in the monoclinic space group P2₁/n [a = 14.7858(2), b = 16.9090(1), c = 26.2350(2)Å; β = 92.861(1)°], aquadi(o‐sulfobenzimidato‐N)bis(4‐propylpyridine)copper(II) ( 2 ) in the tetragonal space group P4₂/n [a = 15.4127(1), c = 13.4604(1)Å], diaquatetrakis(3‐(2‐propenyl)imidazole)copper(II) di‐o‐sulfobenzimidate ( 3b ) in the monoclinic space group P2₁/c [a = 9.3959(5), b = 28.029(2), c = 8.8763(3)Å; β = 111.175(1)°] and di(o‐sulfobenzimidato)tetra(isoquinoline)copper(II) ( 4b ) in the orthorhombic space group Pna2₁ [a = 23.2132(6), b = 11.5760(2), c = 17.6297(4)Å]. The copper atom in 1 is six‐coordinate in a distorted trans‐N₄O₂Cu octahedron with elongated copper—oxygen bonds [Cu—O_water = 2.462(3), Cu—O_sulfonyl = 2.567(3)Å]. This adduct represents the first example of a combined O_sulfonyl/ionic coordination of the o‐sulfobenzimidate ion in the same crystal. The copper atom in 2 is five‐coordinate in the form of a N₄OCu square pyramid [Cu—O_water = 2.238(5)Å]. In 3 , the o‐sulfobenzimidate anions are linked to the copper atom through the coordinated water molecule forming a distorted octahedral N₄O₂Cu environment. In 4 , the copper atom is nearly octahedrally coordinated by four nitrogen atoms and a pair of o‐sulfobenzimidate carbonyl oxygen atoms. The structural details of the o‐sulfobenzimidate coordination pattern correspond well with the 298 and 77 K FT IR spectra of the adducts. The structures of two other solid adducts, tris(3‐(2‐propenyl)imidazole)copper(II) di‐o‐sulfobenzimidate trihydrate ( 3a ) and diaquabis(o‐sulfobenzimidato‐N)bis(isoquinoline)copper(II) ( 4a ) have been predicted by their spectral features. Alteration of the o‐sulfobenzimidate coordination mode upon changing the heterocycle ligand shows that this moiety is as a convenient polyfunctional structural tool for the construction of functional solids.     

Two‐Dimensional Monovalent Copper Halide Coordination Polymers Incorporating Anti‐Conformation 3,3′‐Bipyridine

Hydrothermal treatment of aqueous mixtures of copper(II) halides and 3,3′‐bipyridine (3,3′‐bpy) has afforded the coordination polymers [CuCl(3,3′‐bpy)]_n ( 1 ) and [Cu₂Br₂(3,3′‐bpy)]_n ( 2 ), which were analyzed via single crystal X‐ray diffraction, infrared spectroscopy, and elemental analysis. The structure of 1 consists of two‐dimensional (2‐D) layers constructed from the linkage of castellated one‐dimensional (1‐D) [CuCl]_n stepped chains through anti‐conformation 3,3′‐bpy tethers. Compound 2 presents a related 2‐D sheet motif, albeit built from infinite 1‐D [Cu₂Br₂]_n ladders strutted by 3,3′‐bpy ligands in anti conformation. In both cases neighboring 2‐D sheets stack into 3‐D via weak C–H···halogen interactions.     

Structure and Magnetic Properties of Mononuclear Copper(II) Complexes with 2,2‐Bipyrimidine, 2,3‐Bis(2‐pyridyl)pyrazine,and 4‐Terpyridone Based Ligands

Four new complexes of [Cu(bpm)(ox)(H₂O)] ( 1 ), [Cu(tpd)(dca)(H₂O)] ( 2 ), [Cu(bppz)(N₃)₂] ( 3 ), and [Cu(bpm)₂(μ_1,3‐N₃)(N₃)] ( 4 ) (bpm = 2,2′‐bipyrimidine, bppz = 2,3‐bis(2‐pyridyl)pyrazine, tpd = 4‐terpyridone, dca = dicyanamide, ox = oxalate) have been prepared and characterized by X‐ray single‐crystal analysis and variable‐temperature magnetic measurements. Compounds 1–4 are essentially mononuclear Cu(II) complexes. However, in complex 1 , Cu(II) it was found that intermolecular hydrogen bonding through between H₂O and ox formed 1‐D chain structure. In complex 2 it was found that the hydrogen bonding between H₂O and tpd of the next molecule led to for a binuclear Cu(II) complex. In complex 3 , two nitrogen atoms, one of the pyridyl group of bppz and one of N₃^? ligands, are weakly coordinated to neighbor Cu(II) ion thus leading to formation of a 1‐D chain structure. In complex 4 , one nitrogen atom of terminated N₃^? is weakly coordinated to the neighbor Cu(II) site to form a 1‐D polymeric structure. The magnetic susceptibility measurements indicate that complex 1 and 4 exhibit a weak antiferromagnetic interaction whereas a ferromagnetic coupling has been established for complexes 2 and 3 .     

Syntheses and Structures of Three New Copper(II) Coordination Polymers Involving 2, 2‐(4, 6‐Dinitro‐1, 3‐phenylenedioxy)­diacetic Acid

Three copper(II) coordination polymers, namely, {[CuL(H₂O)₂] · 4H₂O}_n( 1 ), [CuL(H₂O)(DMF)]_n( 2 ), and [CuL(2, 2′‐bipy)(DMSO)] · DMSO ( 3 ) [H₂L = 2, 2′‐(4, 6‐dinitro‐1, 3‐phenyl‐enedioxy)diacetic acid] were synthesized in different solvents (H₂O, DMF, and DMSO). X‐ray single crystal diffraction studies show that both complexes 1 and 3 belong to triclinic crystal system and P$\bar{1}$ space group and complex 2 belongs to the monoclinic crystal system and P2₁/c space group. In three complexes, all the central Cu^II ions coordinate with the ligand, forming a square pyramidal configuration. Both complexes 1 and 2 show similar 1D chain‐like structure and the chains are further connected by hydrogen bonds, forming 3D frameworks. Complex 3 exhibits a 0D structure due to the introduction of the ligand 2, 2′‐bipy. In addition, the luminescence properties of these complexes were investigated.     

Influence of Flexible Bis(benzimidazole) Derivatives on the Self‐assembly of Three Mixed Ligands Silver(I) Coordination Polymers

Three silver(I) coordination polymers namely, [Ag₄(L1)₂(1, 4‐ndc)₂]_n ( 1 ) {[Ag(L2)] · (1, 4‐Hndc) · H₂O}_n ( 2 ), and {[Ag(L3)(H₂O)] · (1, 4‐Hndc)}_n ( 3 ) [L1 = 1, 3‐bis(benzimidazol‐1‐ylmethyl)benzene, 1, 4‐H₂ndc = 1, 4‐naphthalenedicarboxylic acid, L2 = 1, 3‐bis(5, 6‐dimethylbenzimidazole‐1‐ylmethyl)benzene, L3 = 1, 4‐bis(5, 6‐dimethylbenzimidazole)butane], were hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction analysis, elemental analysis, IR spectroscopy, thermogravimetric and XRPD analysis. Complex 1 displays a 1D tube‐like chain, which is packed into a 3D supramolecular network by π–π stacking interactions. Complex 2 features an infinite 1D linear chain. Complex 3 contains a 1D wave‐like chain, which is extended into a 3D supramolecular network through O–H ··· O hydrogen bonding interactions. Moreover, these coordination polymers exhibit catalytic properties for degradation of methyl orange in Fenton‐like processes.     

Three Coordination Polymers based on 3,5‐Bis(imidazole‐1‐yl)pyridine and Benzoic Acid: Synthesis,Crystal Structures and Photoluminescent Properties

Three metal coordination polymers {[Co(L)₂(H₂O)₂]²⁺ · 2NO₃^–}_n ( 1 ), {[Mn(L)₂(H₂O)₂]²⁺ · 2Cl^– · 3H₂O}_n ( 2 ), and [ZnL(ba)₂]_n ( 3 ) [L = 3,5‐bis(imidazole‐1‐yl)pyridine and Hba = benzoic acid] were synthesized and structurally characterized by IR spectroscopy, elemental analysis, X‐ray powder diffraction, and X‐ray single crystal diffraction. Complex 1 shows a one‐dimensional (1D) chain structure. Adjacent chains are connected by hydrogen bonding and nitrate groups to form a 3D network. Complex 2 features a 2D layer structure. A three‐dimensional network is constructed through the cluster consisting of two chloride ions and three water molecules. Complex 3 shows a 1D zigzag chain structure that further twists together to form a 3D network. The X‐ray powder diffraction patterns were compared with the simulated ones. Moreover, the luminescent properties of 1 – 3 were investigated in the solid state at room temperature, and the thermogravimetric analyses were carried out to study the thermal stability of the three complexes.     

Structural Studies of a Copper(II) Complex with Inequivalent 2‐Acetylpyridine 3‐Piperidylthiosemicarbazonato Ligands and a Nickel(II) Complex with Different Modes of Coordination by the Two Thiosemicarbazonato Moieties of 1‐Phenylglyoxal Bis{N(4)‐diethylthiosemicarbazone}

The crystal structure of a copper(II) complex of 2‐acetylpyridine 3‐piperidylthiosemicarbazone, [Cu(Acpip)₂], indicates a tridentate, monoanionic ligand (i. e., pyridine nitrogen, imine nitrogen and thiolato sulfur atoms) and a bidentate, monanionic ligand (i. e., imine nitrogen and thiolato sulfur atoms). The stereochemistry approaches square pyramidal with the bidentate ligand occupying an apical (imine nitrogen atom) and basal (thiolato sulfur atom) position. The structure of a nickel(II) complex of 1‐phenylglyoxal N(4)‐diethylthiosemicarbazone, [Ni(Pg4DE)], has a 4‐6‐5 trichelate system rather than the 5‐5‐5 system common to bis(thiosemicarbazones). Coordination of the hydrazinic nitrogen atom of the “phenyl arm” along with the thiolato sulfur atom provides the 4‐membered chelate ring.     

A Luminescent Silver(I) Metal‐Organic Framework with New (4,6)‐Connected Topology Based on Mixed Tetrachlorotereph­thalate and 2,2′‐Bipyridine Ligands

A silver(I) coordination polymer with mixed 2,3,5,6‐tetrachloro‐1,4‐benzenedicarboxylate (BDC‐Cl₄) and 2,2′‐bipyridine (2,2′‐bpy) ligands, [Ag₂(BDC‐Cl₄)(2,2′‐bpy)]_n ( 1 ), was synthesized and structurally characterized. Compound 1 features a robust three‐dimensional (3D) network, exhibiting a new (4,6)‐connected net with the Schläfli symbol of (3² · 4² · 5 · 6)₂(3² · 4² · 5² · 8⁷ · 9 · 10). The photoluminescence properties of 1 were investigated in the solid state at room temperature.