One-dimensional silver(I) 5,5-diethylbarbiturato coordination polymers with N-piperidineethanol and 1,3-bis(4-piperidyl)propane: Syntheses,crystal structures,spectroscopic and thermal properties

Two new coordination polymers, [Ag₂(barb)(pipet)]_n (1) and {Na₃[Ag₂(barb)₂](pippr)·2H₂O}_n (2) (where H₂barb, pipet and Hpippr are 5,5-diethylbarbituric acid, N-piperidineethanol and 1,3-bis(4-piperidyl)propane, respectively) have been synthesized and characterized by elemental analysis, IR, thermal analysis and X-ray single-crystal diffraction techniques. Silver(I) ions in complexes 1 and 2 are bridged by barb dianions, leading to one-dimensional coordination polymers. In 1, the barb ligand acts as a tetradentate bridging ligand, while in 2 as a bidendate bridging ligand. The pipet ligand behaves as a bidentate chelating donor, whereas the pippr anion is not involved in coordination and remains as a counter-ion. The one-dimensional chains of 1 and 2 are further extended into supramolecular networks. Spectral and thermal analysis data for 1 and 2 are in agreement with the crystal structures.     

Syntheses,structures and luminescent properties of four copper(I) cyanide coordination polymers based on 2-(n-pyridyl)benzimidazole ligands (n = 2, 3, 4)

Four copper(I) cyanide coordination polymers containing 2-(n-pyridyl)benzimidazole ligands, namely [Cu₂(CN)(2-PyBIm)]_n (1), [Cu₂(CN)₂(3-PyHBIm)]_n (2), {[Cu₃(CN)₃(4-PyHBIm)₄] · 2H₂O}_n (3) and [Cu₅(CN)₃(4-PyBIm)₂]_n (4), have been synthesized and characterized by X-ray crystallography. Complex 1 is a one-dimension coordination polymer in which 2-(2-pyridyl)benzimidazole is deprotonated and adopts a bridging tridentate coordination mode. Complex 2 has ladder-like structure in which 2-(3-pyridyl)benzimidazole does not deprotonate and acts as a bidentate bridge. Complex 3 displays a saddle-shaped helical chain constructed through μ₂-cyanide group and the outstretched neutral 2-(4-pyridyl)benzimidazole monodentate ligand. Complex 4 shows two-dimension layer polymeric structure in which deprotonated 2-(4-pyridyl)benzimidazole acts as a tridentate bridging ligand. The cyanide groups in four complexes all act as bidentate bridging ligands. These complexes are thermal stable and display luminescence in the solid states.     

Syntheses and characterization of novel lanthanide adamantine-dicarboxylate coordination complexes

Hydrothermal reactions of 1,10-phenanthroline (phen), 1,3-adamantanedicarboxylic acid (H₂L) and lanthanide chlorides yielded six compounds: [Ln(L)(HL)(phen)] (Ln=Pr, 1; Nd, 2), [Ln(L)(HL)(phen)(H₂O)] (Sm, 3; Eu, 4), [Tb(L)(HL)(phen)(H₂O)]₂·2H₂O (5), [Er₃(L)₄(OH)(phen)]₂ (6). Compounds 1-4 are structurally featured by one-dimensional polymeric chains; 5 hold binuclear structure constructed from eight-coordinated lanthanide center LnN₂O₆ of distorted bicapped trigonal prism bridged by dicarboxylate ligands; 6 shows that erbium ions are in mono and bicapped trigonal prismatic geometries, respectively, which are further connected by μ₃-OH to give rise to trinuclear structure. Thermogravimetric analyses of 1, 3 and 5 were performed. Fluorescent measurements of 4 and 5 were carried out, respectively.     

A systematic investigation of the CuCl2/H2mal/phen reaction system (H2mal = malonic acid): Solution and solid state studies of its products

The systematic investigation of the parameter space of the CuCl₂/H₂mal/phen reaction system in MeOH resulted in the isolation of seven different complexes either as mixtures or in pure form, six of which have been structurally characterized. The molar ratios of the reactants and the crystallization methods have been systematically varied, leading to the isolation of compounds [Cu(H₂O)(phen)(mal)] (1), [Cu(MeOH)(phen)(mal)] (2), [Cu₂Li₂Cl₂(phen)₂(mal)₂(MeOH)₄] (3), [Cu₂(phen)₄(mal)][CuCl(phen)(mal)](OH) (4), [CuCl(phen)₂]Cl (5), and [CuCl(phen)(mal)][CuCl(phen)₂][Cu(phen)₂(Hmal)]Cl (6). The coordination versatility of the malonato ligand has been confirmed by the presence of three different coordination modes and its two deprotonation states in compounds 1–6. Solution studies on methanolic solutions of 2–4 and 6 by mass spectrometry revealed the absence of parent ion peak and the presence of fragment ions of low relative abundance not previously found in their crystal structure, thus indicating decomposition and rearrangement/reorganization of the complexes in solution and confirming the dynamic character of their solutions. Compounds 3 and 4 have been also studied in the solid state by EPR spectroscopy and magnetic measurements.     

Complexes derived from the copper(II)/succinamic acid/N,N′,N″-chelate tertiary reaction systems: Synthesis,structural and spectroscopic studies

The use of succinamic acid (H₂sucm) in Cu^II/N,N′,N″-donor [2,2′:6′,2″-terpyridine (terpy), 2,6-bis(3,5-dimethylpyrazol-1-yl)pyridine (dmbppy)] reaction mixtures yielded compounds [Cu(Hsucm)(terpy)]_n(ClO₄)_n (1), [Cu(Hsucm)(terpy)(MeOH)](ClO₄) (2), [Cu₂(Hsucm)₂(terpy)₂](ClO₄)₂ (3), [Cu(ClO₄)₂(terpy)(MeOH)] (4), [Cu(Hsucm)(dmbppy)]_n(NO₃)_n·3nH₂O (5^.3nH₂O), and [CuCl₂(dmbppy)]·H₂O (6·H₂O). The succinamate(−1) ligand exists in four different coordination modes in the structures of 1–3 and 5, i.e., the μ₂-κO:κO′:κO″ in 1 and 5 which involves asymmetric chelating coordination of the carboxylato group and ligation of the amide O-atom leading to 1D coordination polymers, the μ₂-κ²O:κO′ in 3 which involves asymmetric chelating and bridging coordination of the carboxylato group, and the asymmetric chelating mode in 2. The primary amide group, either coordinated in 1 and 5, or uncoordinated in 2 and 3, participate in hydrogen bonding interactions, leading to interesting crystal structures. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the Hsucm⁻ ligands. The thermal decomposition of complex 5·3nH₂O was monitored by TG/DTG and DTA measurements.     

Synthetic,structural and spectroscopic studies of complexes derived from the copper(II) perchlorate/fumaric acid/N,N′-chelates tertiary reaction systems

The synthetic investigation of the Cu(ClO₄)₂·6H₂O/fumaric acid (H₂fum)/N,N’-chelates (1,10-phen, 2,2′-bpy) tertiary reaction systems has yielded mononuclear, dinuclear and tetranuclear complexes, and three coordination polymers. The chemical and structural identity of the products depends on the solvent, the absence or presence of external hydroxides in the reaction mixtures and the N,N’-donor. Three fumarato(−2) complexes, i.e. compounds [Cu₂(fum)(phen)₄](ClO₄)₂·2H₂O (1·2H₂O), [Cu(fum)(phen)(H₂O)]_n (3) and [Cu₂(fum)(bpy)₂(H₂O)₂]_n(ClO₄)_2n (6), were isolated and structurally characterized, and four non-fumarato complexes, i.e. compounds [Cu₄(μ₃-ΟΗ)₂(μ₂-ΟΗ)₂(phen)₄(H₂O)₂](ClO₄)₄·2H₂O (2·2H₂O), [Cu(ClO₄)(phen) (MeCN)₂(H₂O)](ClO₄) (4), [Cu(ClO₄)(phen)(MeCN)₂]_n(ClO₄)_n (5) and [Cu(ClO₄)₂(bpy)(MeCN)₂] (7), were simultaneously obtained from the reaction systems investigated. The coordination versatility of the fumarato(−2) ligand is reflected to the three different coordination modes observed in 1·2H₂O, 3 and 6; the monodentate bridging μ₂-κO:κO′ mode in 3, the asymmetric chelating bridging μ₂-κO:κO′:κO′′:κO′′′ mode in 1·2H₂O and 3, and the syn,syn bridging μ₄-κO:κO′:κO′′:κO′′′ mode in 6. The crystal structures of the complexes are stabilized by intra- and inter-molecular hydrogen bonding and π–π stacking interactions leading to interesting supramolecular architectures. Characteristic IR bands of the complexes are discussed in terms of the known structures, and the coordination modes of the fum²⁻ ligands.     

Synthesis and coordination chemistry of new tetradentate N2S2 donor Schiff-base ligand ca2-dapte: Mononuclear and dinuclear copper(I) complexes [Cu(ca2dapte)]ClO4 and [{Cu(PPh3)(X)}2(ca2dapte)] (X = I and Br)

A mononuclear copper(I) complex, [Cu(ca₂dapte)]ClO₄ (1), and two dinuclear copper(I) complexes, [{Cu(PPh₃)(X)}₂(ca₂dapte)] (X = I (2) and Br (3)), of a new tetradentate N₂S₂ donor Schiff-base ligand ca₂dapte have been prepared (ca₂dapte = N,N′-bis(trans-cinnamaldehyde)-1,2-di(o-iminophenylthio)ethane). These compounds have been characterized by elemental analyses (CHN), FT-IR, UV–Vis and ¹H NMR spectroscopy. The crystal structures of these copper(I) complexes have been determined by single-crystal X-ray diffraction. The coordination geometry around Cu(I) centers in these complexes is a distorted tetrahedron. The ca₂dapte is coordinated to Cu(I) as a tetradentate ligand in 1, while it acts as a bis-bidentate bridging ligand in 2 and 3.     

Synthesis and crystal structure of two copper complexes with one-dimensional chain structures bridged by bipyridine ligands

Two copper complexes {[Cu(phen)(azpy)(H₂O)(ClO₄)](ClO₄)}_n1 (phen=1,10-phenthroline, azpy=4,4′-azobispyridine) and {[Cu(phen)(bpe)(H₂O)(ClO₄)](ClO₄)}_n2 (bpe=trans-1,2-bis(4-pyridyl)ethylene), have been synthesized and characterized. The X-ray analysis reveals that copper ion has distorted square pyramidal coordination environments in the complexes 1 and 2. The copper is coordinated by two N atoms of phen, two N atoms from two bridging ligand azpy in 1 and from two bridging ligand bpe in 2, one O atom of coordinated water. Due to Jahn Teller distortion the sixth site in 1 and 2 is occupied by one O atom from one perchlorate anion. Copper ions are linked to each other through bridging ligand azpy in 1 and bridging ligand bpe in 2 to form one-dimensional chain. Variable-temperature magnetic susceptibility studies show that there is a weak antiferromagnetic interaction between the Copper ions in 1 and 2.     

Novel octahedral nickel(II) dithiocarbamates with bi- or tetradentate N-donor ligands: X-ray structures of [Ni(Bzppzdtc)(phen)2]ClO4 · CHCl3 and [Ni(Bz2dtc)2(cyclam)]

A series of novel octahedral nickel(II) dithiocarbamate complexes involving bidentate nitrogen-donor ligands (phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine) or a tetradentate ligand (cyclam = 1,4,8,11-tetraazacycloteradecane) of the composition [Ni(BzMetdtc)(phen)₂]ClO₄ (1), [Ni(Pe₂dtc)(phen)₂]ClO₄ (2), [Ni(Bzppzdtc)(phen)₂]ClO₄ · CHCl₃ (3), [Ni(Bzppzdtc)(phen)₂](SCN) (4), [Ni(BzMetdtc)(bpy)₂]ClO₄ · 2H₂O (5), [Ni(Pe₂dtc)(cyclam)]ClO₄ (6), [Ni(BzMetdtc)₂(cyclam)] (7), [Ni(Bz₂dtc)₂(cyclam)] (8) and [Ni(Bz₂dtc)₂(phen)] (9) (BzMetdtc = N,N-benzyl-methyldithiocarbamate(1-) anion, Pe₂dtc = N,N-dipentyldithiocarbamate(1-) anion, Bz₂dtc = N,N-dibenzyldithiocarbamate(1-) anion, Bzppzdtc = 4-benzylpiperazinedithiocarbamate(1-) anion), have been synthesized. Spectroscopic (electronic and infrared), magnetic moment and molar conductivity data, and thermal behaviour of the complexes are discussed. Single crystal X-ray analysis of 3 and 8 confirmed a distorted octahedral arrangement in the vicinity of the nickel atom with a N₄S₂ donor set. They represent the first X-ray structures of such type complexes. The catalytic influence of complexes 2, 3, 6, and 7 on graphite oxidation was studied and discussed.     

Crystal structures and properties of four coordination polymers constructed from flexible pamoic acid

Four novel coordination polymers constructed from flexible pamoic acid, namely [Co(pam)(4,4′-bipy)]_n·nH₂O (1), [Ni(pam)(4,4′-bipy)(H₂O)₂]_n·2nCH₃CN (2), [Cd(pam)(py)₂]_n·npy (3) and [Mn₂(pam)₂(py)₆(H₂O)₂]_n·2npy (4), (H₂pam = pamoic acid, 4,4′-bipy = 4,4′-bipyridine, py = pyridine), have been synthesized and characterized by elemental analysis, infrared spectra and X-ray crystallography. Complex 1 is a 2-D coordination polymer constructed from chelating bis-bidentate pam and 4,4′-bipyridine bridging ligands. Complex 2 is a 2-D coordination polymer assembled by bis-monodentate pam and 4,4′-bipyridine, where acetonitrile is filled in the rectangle channels. Both 2-D coordination polymers display undulated (4,4) grid layers as sql topology. Complex 3 displays a 1-D polymeric chain using chelating bis-bidentate pam as bridging ligand. Complex 4 exhibits an interesting bis-monodentate pam-Mn(II) 1-D polymeric chain, in which exist two-type six-coordinated manganese centers. Mn(1) is bound to four pyridine ligands, whereas Mn(2) is combined to two pyridine and two H₂O molecules. Their thermal stabilities have been investigated. Cadmium complex 3 displays strong green luminescence with emission maximum at 543 nm.     

pH- and mol-ratio dependent formation of zinc(II) coordination polymers with iminodiacetic acid: Synthesis, spectroscopic, crystal structure and thermal studies

Three novel zinc coordination polymers (NH₄)_n[Zn(Hida)Cl₂]_n (1), [Zn(ida)(H₂O)₂]_n (2), [Zn(Hida)₂]_n·4nH₂O (3) (H₂ida=iminodiacetic acid) and a monomeric complex [Zn(ida)(phen)(H₂O)]·2H₂O (4) (phen=1,10-phenanthroline) have been synthesized and characterized by X-ray diffraction methods. 1 and 2 form one-dimensional (1-D) chain structures, whereas 3 exhibits a three-dimensional (3-D) diamondoid framework with an open channel. The mononuclear complex 4 is extended into a 3-D supramolecular architecture through hydrogen bonds and π-π stacking. Interestingly, cyclic nonplanar tetrameric water clusters are observed that encapsulated in the 3-D lattice of 4. Based on ¹H and ¹³C NMR observations, there is obvious coordination of complex 2 in solution, while 1 and 3 decompose into free iminodiacetate ligand. Monomer [Zn(ida)(H₂O)₃] (5) is considered as a possible discrete species from 2. These coordination polymers can serve as good molecular precursors for zinc oxide.     

Four triazole-bridging coordination polymers containing (m-phenol)-1,2,4-triazole: Syntheses, structures and properties of fluorescence and magnetism

Four triazole-bridging coordination complexes, [Zn₄(ptr)₂(SO₄)₃(μ₃-OH)₂(H₂O)₄]_n (1), [Hg(CN)₂(ptr)]_n (2), [Hg(Cl)₂(ptr)]_n (3), and [Cu₂(μ₂-ptr)₂(μ₂-F)₂]_n(SiF₆)_n·2nH₂O (4), were synthesized with (m-phenol)-1,2,4-triazole (ptr). Compounds 1-4 with extended structures of 4-substituted 1,2,4-triazole are rarely reported. The layered structure of 1 can be regarded as constructed from the 2-D inorganic backbone of SO₄²⁻(2) anions bridging [Zn₄(μ₃-OH)₂(H₂O)₂]⁶⁻ subunits with the ptr ligands anchoring to both sides of backbone. Compounds 2 and 3 are the first mercury(II) complexes with 4-substituted 1,2,4-triazole, which feature the ptr ligand acting as a bidentate ligand bridging the Hg(II) atoms to form arciform -Hg-ptr-Hg-ptr chains. The structure of 4 is constructed from the F atoms bridging Cu atoms in symmetrical μ₂-coordination mode to form a zigzag cationic chain with each ptr ligand bridging a pair of Cu atom on the both sides, resulting in a nonplanar 5-membered [Cu₂N₂F] ring. Fluorescent properties of 1-4 were characterized and the magnetic property of 4 shows antiferromagnetic interaction between the copper(II) ions.     

Synthesis and characterization of rigid +2 and +3 heteroleptic dinuclear ruthenium(II) complexes

Synthesis and characterization of the dinuclear ruthenium coordination complexes with heteroleptic ligand sets, [Cl(terpy)Ru(tpphz)Ru(terpy)Cl](PF₆)₂(7) and [(phen)₂Ru(tpphz)Ru(terpy)Cl](PF₆)₃(8), are reported. Both structures contain a tetrapyrido[3,2-α:2′,3′-c:3′′,2′′-h:2′′,3′′-j]phenazine (tpphz) (6) ligand bridging the two metal centers. Complex 7 was obtained via ligand exchange between, RuCl₂(terpy)DMSO (5) and a tpphz bridge. Complex 8 was obtained via ligand exchange between, [Ru(phen)₂tpphz](PF₆)₂(4) and RuCl₂(terpy)DMSO (5). Metal-to-ligand-charge-transfer (MLCT) absorptions are sensitive to ligand set composition and are significantly red-shifted due to more electron donating ligands. Complexes 7–9 have been characterized by analytical, spectroscopic (IR, NMR, and UV–Vis), and mass spectrometric techniques. The electronic spectral properties of 7, 8, and [(phen)₂Ru(tpphz)Ru(phen)₂](PF₆)₄(9), a previously reported +4 analog, are presented together. The different terminal ligands of 7, 8, and 9 shift the energy of the MLCT and the π–π* transition of the bridging ligand. These shifts in the spectra are discussed in the context of density functional theory (DFT). A model is proposed suggesting that low-lying orbitals of the bridging ligand accept electron density from the metal center which can facilitate electron transfer to nanoparticles like single walled carbon nanotubes and colloidal gold.     

Preparation of three terbium complexes with p-aminobenzoic acid and investigation of crystal structure influence on luminescence property

Three new rare earth p-aminobenzoic acid complexes, [Tb₂L₆(H₂O)₂]_n (1), [Tb₂L₆(H₂O)₄]·2H₂O (2) and [Tb(phen)₂L₂(H₂O)₂](phen)L·4H₂O (3) (HL: p-aminobenzoic acid; phen: 1, 10-phenanthroline), with different structural forms are reported in this paper. Complex 1 is a polymolecule with a two-dimensional plane structure. Compound 2 is a binuclear molecule, and 3 appears to be a mononuclear complex. The fluorescence intensity, the fluorescence life-time and emission quantum yield of 2, which has two coordination water molecules, is better than those of 1, which has only one coordination water molecule. This is an unusual phenomenon for general fluorescent rare earth complexes. The fluorescence performance of 3 is the most unsatisfactory among the three complexes. Their crystal structures show that the coordination mode of the ligand is an important factor influencing the luminescence properties of a fluorescent rare earth complex.     

μ-Coordination chemistry of NO ligands: Adducts of trans-Mo(dmpe)2(H)(NO) with lithium salts

Four adducts were formed by the reaction of trans-Mo(dmpe)₂(H)(NO) (1) (dmpe = bis(dimethylphosphino)ethane) and a respective lithium reagent to afford, [Mo(dmpe)₂(H)(NO)LiHBEt₃]₂ (2), [Mo(dmpe)₂(H)(NO)LiN(SiMe₃)₂]₂ (3), [Mo(dmpe)₂(H)(NO)]₃(LiBH₄)₂ (4), and {[Mo(dmpe)₂(H)(NO)]₂[LiBH₄]₅}_n (5). Structures 2-5 were characterized by crystal X-ray diffraction analyses. Structures 2 and 3 revealed to be dimers of the 1:1 adduct of 1 and the lithium salt. The two nitrosyl oxygen atoms in 2 are μ₂-bridged connecting two separate LiHB(C₂H₅)₃ moieties, whereas in 3 these oxygen atoms exhibit a terminal coordination mode binding to two lithium ions of the dimeric [LiN(SiMe₃)₂]₂ unit. Structure 4 shows a discrete structure formed by two separate mononuclear LiBH₄ units being bridged by the nitrosyl oxygen atoms of three Mo(dmpe)₂(H)(NO) moieties. Structure 5 displays a complicated chain structure with differently coordinated lithium centers, various types of bridging BH₄ and bridging nitrosyl groups.     

Two- and three-dimensional aliphatic dicarboxylate copper coordination polymers with bis(3-pyridylmethyl)piperazine tethers

Divalent copper coordination polymers containing aliphatic dicarboxylate and bis(3-pyridylmethyl)piperazine (3-bpmp) tethering ligands exhibit different topologies depending on the length of the polymethylene chain and stoichiometric ratio. {[Cu(succinate)(3-bpmp)]·8H₂O}_n (1) and {[Cu(adipate)(3-bpmp)(H₂O)]·10H₂O}_n (4) both display (4,4) rhomboid grids, although the latter shows significant undulations to accommodate the additional girth of the dicarboxylate tethers. [Cu₂(succinate)₂(3-bpmp)_0.5(H₂O)]_n (2) and [Cu₂(glutarate)₂(3-bpmp)]_n (3) possess {Cu₂(OCO)₃} partial paddlewheel and {Cu₂(OCO)₄} complete paddlewheel carboxylate bridged dimeric units, respectively. However, 2 has a (6,3) brick-layered structure with a rare binodal moganite (mog) supramolecular topology, while 3 possesses a non-interpenetrated primitive cubic network. Intriguing co-crystallized water tapes are seen in 1 and 4. Thermal dehydration and decomposition behavior of 1–4 is also presented.     

Five novel transition metal coordination polymers with 2D/3D framework structure based on flexible H2tzda and ancillary ligand bpe

Five new transition metal coordination polymers based on H₂tzda and co-ligand bpe, {[M(tzda)(bpe)]·H₂O}_n [M=Zn(1), Cd(2), Mn(3), Co(4)] and [Ni₂(tzda)₂(bpe)₂(H₂O)]_n (5) [H₂tzda=(1,3,4-thiadiazole-2,5-diyldithio)diacetic acid, bpe=1,2-bis(4-pyridyl)ethane], have been hydrothermally synthesized and structurally characterized. Compounds 1-4 feature a 2D-layered architecture generated from [M(tzda)]_n moiety with double-chain structure cross-linking bpe spacers. However, the conformations bpe adopts in 3 and 4 are different from those in 1 and 2 due to the rotation of C-C single bond in bpe. Polymer 5 exhibits an interesting 3D porous framework with 2-fold interpenetration, in which intriguing 1D double helix chains are observed. The photoluminescence properties of 1 and 2 in the solid-state at room temperature are investigated. In addition, variable-temperature magnetic data show weak antiferromagnetic behavior in 3-5.     

Characterization of three new divalent zinc coordination polymers involving fluorinated carboxylate tecton via the modulation of heterocyclic N-donor co-ligands

Three new fluorous coordination polymers with a fluorinated carboxylate tecton and N-donor co-ligands, {[Zn₂(hfipbb)₂(phen)₂]·2H₂O}_n (1), [Zn₂(hfipbb)₂(bipy)(H₂O)]_n (2), and [Zn₅(hfipbb)₄ (Hhfipbb)₂ (bpp)]_n (3), [H₂hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid), phen = 1,10-phenthroline, bipy = 4,4′-bipyridine, and bpp = 1,3-bi(4-pyridyl)propane], have been prepared and characterized by elemental analysis, IR spectra, and X-ray diffraction. Compound 1 exhibits a 3D supramolecular network assembled from two independent 1D chain motifs [Zn(hfipbb)(phen)] through π?π stacking, and C-H?F and O-H?O interactions. Compound 2 features 2D undulating layer structure with 4⁴-sql network. Whereas, in compound 3, pentanuclear [Zn₅(η²-O)₂(μ²-η¹:η¹-CO₂)]²⁻ cores are bridged by hfipbb²⁻ and bpp ligands into a 3D 6-connected sxd framework with a point symbol of (3³·4⁶·5⁵·6). The diverse arrangements of the compounds show the modulation of the heterocyclic N-donor co-ligands can suitably mediate the coordination requirement of metal centers as well as the binding modes of fluorinated carboxylate tecton, which consequently generate diverse crystalline architectures. In addition, the properties of thermogravimetric analysis, X-ray powder diffraction, and photoluminescent behaviors of the compounds have also been discussed.     

Syntheses,structures, network topologies and photoluminescence of four Zn(II) and Cd(II) coordination polymers based on 5-carboxyl-1-carboxymethyl-2-oxidopyridinium

5-Carboxyl-1-carboxymethyl-2-oxidopyridinium (H₂CCOP) and a combination of N-donor ligands, such as 4,4′-bipyridine (4,4′-bipy) and 1,10-phenanthroline (phen) with d¹⁰ metal ions Zn(II) and Cd(II) give rise to four coordination polymers, namely, [Zn₂(CCOP)(OH)₂(H₂O)] (1), [Zn(CCOP)(phen)(H₂O)]·H₂O (2), [Cd(CCOP)(H₂O)₂]·3H₂O (3), and [Cd(CCOP)(H₂O)] (4). Polymer 1 features an unusual bilayer motif and forms the final (3,8)-connected 3D topology by hydrogen bonds. Polymer 2 consists of one-dimensional (1D) chains which are further connected with each other via hydrogen bonds to form the final interesting (3,6)-connected rutile network. Polymer 3 is made up of an unusual 2D structure containing cylinder channels in the b axis and features the (4,4)-connected 3D network by hydrogen bonds. Polymer 4 presents an interesting uninodal 4-connected net compared to polymer 3. These four coordination polymers are obtained by evaporation or hydrothermal route and characterized by analytical, spectroscopic, and crystallographic methods. Photoluminescence studies revealed that these four coordination polymers display structure-related fluorescent emission bands (λ_ex = 342 nm) at 361 nm for polymer 1, 404 nm for polymer 2, 367 nm for polymer 3, and 371 nm for polymer 4 in the solid state at room temperature.     

Syntheses and crystal structures of manganese,nickel and zinc chloride complexes with dimethoxyethane and di(2-methoxyethyl) ether

Reactions of manganese and zinc chloride with dimethoxyethane (DME) in the presence of (CH₃)₃SiCl and water resulted in [MnCl₂(DME)]_n (1) with a polymeric chain structure and in the molecular [ZnCl₂(DME)]₂ (2), respectively. The complexes 1 and 2 reacted with di(2-methoxyethyl) ether (abbreviated diglyme) in tetrahydrofuran (THF) solvent achieving binuclear [MnCl₂(diglyme)]₂ (3) and mononuclear [ZnCl₂(diglyme)] (4), respectively. The complex [NiCl₂(diglyme)]₂ (5) was prepared by the reaction of nickel chloride hexahydrate, diglyme and (CH₃)₃SiCl in THF solvent. A distorted octahedral geometry was found for manganese and nickel ions in the complexes 1, 3 and 5. Linear chains of manganese ions linked by double chloride bridges are present in 1. Two bridging chlorides connect two manganese or nickel atoms into isostructural binuclear molecules 3 and 5, respectively. Two zinc ions in the complex 2 are in different environments, in a tetrahedral and in an octahedral one, while five-coordinate zinc ions are present in the mononuclear complexes 4.