A Facile Access to New Polymethylmethacrylate-Anchored Ferrocene Substituted Nickel(II) Unsymmetrical Schiff Base Complexes: Synthesis and Characterization

This paper discloses two new side-chain metallopolymers containing an unsymmetrical organometallic Schiff base complex of Ni(II) linked to a polymethylmethacrylate (PMMA) matrix. The neutral ferrocene substituted Schiff base complex 1, Ni{CpFe(η⁵-C₅H₄)-C(O)CH=C(CH₃)N–o-C₆H₄N=CH-(2-O,5-OH-C₆H₃)} where (Cp = η⁵-C₅H₅), was synthesized via template reaction by condensation of the tridentate half-unit metalloligand Fc-C(O)CH=C(CH₃)-N(H)-o-C₆H₄NH₂ (Fc = ferrocenyl = CpFe(η⁵-C₅H₄)) with 2,5-dihydroxybenzaldehyde in the presence of nickel(II) acetate tetrahydrate. The binuclear Schiff base complex of Ni(II) containing an aromatic free hydroxyl group was reacted under basic conditions with PMMA to afford, upon trans-esterification reaction, metallopolymers 2 (complex 1 monomeric unit/PMMA = 1/5) and 3 (complex 1 monomeric unit/PMMA = 1/3). Elemental analysis, FT-IR, ¹H and ¹³C NMR spectroscopies, and cyclic voltammetry were utilized to characterize the newly synthetized compounds. Surface morphology of the metallopolymer film of 2 was studied using atomic force microscopy.     

Linear Coordination Polymers Assembled from Dinuclear Cu(I) Units: Interchain π–π and CH–π Interactions in Controlling Alignments of Polymeric Chains in Solid State

An axial substitution of the coordinated acetonitrile molecules in dinuclear Cu(I) compound, [Cu₂(μ-PhPPy₂)₂(CH₃CN)₂](ClO₄)₂ (1) (PhPPy₂ = bis(2-pyridyl)phenylphosphine) by various dicarboxylates (isophthalate, terephthalate and naphthalene-2,6-dicarboxylate) led to a class of new linear coordination polymers, {[Cu₂(μ-PhPPy₂)₂](μ-1,3-C₆H₄(CO₂)₂)}_∞ (2), {[Cu₂(μ-PhPPy₂)₂](μ-1,4-C₆H₄(CO₂)₂)}_∞ (3) and {[Cu₂(μ-PhPPy₂)₂](μ-2,6-C₁₂H₆(CO₂)₂)}_∞ (4). X-ray crystallographic studies reveals that all the polymers adopt almost linear structures, where the dicarboxylate groups connect dinuclear Cu(I) units as linkers. In 2 and 4, polymeric chains are parallel to each other. However the chains in 3 are arranged layer by layer, where polymeric chains are parallel in one layer, but chains in the neighboring layers are aligned with the angle (42°). The detailed structural analyses demonstrate that in solid state, the polymeric chains display different orientations which are controlled by interchain π–π and CH–π interactions. In solid state, all the coordination polymers are highly emissive at room temperature, which exhibit phosphorescence characteristics and are assigned as metal to ligand charge transfer.     

Structure,Luminescence, and Vapochromism of Bridged Cationic Copper(I) Dimers and Polymers

The dimeric complex of Cu(I) [Cu₂(PPh₃)₄(MeCN)₂(Bpy)](BF₄)₂ (1a, Bpy = 4,4′-dipyridyl) self-assembles in CH₂Cl₂ or acetone and shows intense photoluminescence (excitation λ_max = 356 nm, emission λ_max = 486 nm, ? = 0.47). The MeCN ligands are readily removed from 1a, producing [Cu₂(PPh₃)₄(Bpy)](BF₄)₂ (1b) and altering the photophysical behavior (excitation λ_max = 336 nm, emission λ_max = 568 nm, ? = 0.07). The desolvated compound 1b reversibly absorbs many vapor phase nucleophiles, as revealed by thermogravimetry. Intense luminescence emission is restored for 1b/Nu, Nu = MeCN (1a), acetone, tetrahydrothiophene (THT), and Et₂S. Films of 1b are produced when CH₂Cl₂ solutions of 1a are cast onto glass. The films also react with Nu vapor, again producing intense emission. The pyrazine-bridged dimer [Cu₂(PPh₃)₄(MeCN)₂(Pyz)](BF₄)₂ (2a) is produced in CH₂Cl₂, while [Cu₂(PPh₃)₄(MeCN)(acetone)(Pyz)](BF₄)₂?½[Cu₂(PPh₃)₄(MeCN)₂(Pyz)](BF₄)₂ (2b) is formed in acetone. The crystal structure of the polymer {[Cu(PPh₃)₂(Bpy)](BF₄)?acetone} _n (3) is reported, as is the mixed polymer/dimer structure {[Cu(PPh₃)₂(Pyz)](BF₄)} _n ?½n[Cu₂(PPh₃)₄(BF₄)₂(Pyz)] (4b) in which the dimer units show Cu–FBF₃ coordination. The Pyz dimer and the Pyz and Bpy polymers show much weaker luminescence behavior than that of Bpy dimers 1a and the related 1b/Nu adducts. Nucleophile adduct structures [Cu₂(PPh₃)₄(THT)₂(Bpy)](BF₄)₂?½ethyl ether (5) and [Cu₂(PPh₃)₄(Py)₂(Bpy)](BF₄)₂?CH₂Cl₂ (6) confirmed the coordination of one Nu per Cu to 1b.     

Structural, Theoretical and Multinuclear NMR Study of a New Polymeric Mercury(II) Complex with an Ambidentate Phosphorus Ylide

The reactions of phosphorus ylides of the type Ph₃P=C(H)C(O)R [R = 2,4-dichlorophenyl (L ¹ ) and 4-isopropylphenyl (L ² )] with HgX₂ [X = Cl (1, 4), Br (2, 5) and I (3, 6)] salts using methanol as a solvent are reported. Single crystal X-ray analysis carried out on L ¹ , 2 and 3 and reveals the presence of a novel polymeric structure for 2 and a centrosymmeteric dimeric structure for 3. The complexes have been studied by elemental analyses, IR, ¹H and ³¹P NMR spectroscopy. On the basis of DFT calculations, the formation of [Hg₂Br₆]^2? anions in 2 has a key role in the formation of the polymeric structure; and, the formation of [Hg₂L₂I₄] molecule thermodynamically is about 25 kcal/mol more favorable than the corresponding [Hg₂L₂Br₄] molecule.     

Salen Type Homo-multinuclear Yb3 and Yb4 Complexes and Their NIR Luminescence

Two discrete salen type homo-multinuclear Yb₃ and Yb₄ complexes, namely, [Yb₃L₃(OAc)₃]·3CH₃OH·H₂O (1) and [Yb₄L₂(OAc)₄(μ₃-OH)₂(H₂O)₂](ZnCl₄)·3CH₃OH (2) (H₂L = N,N′-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine) have been synthesized by reactions of H₂L and different ytterbium salts. X-ray crystallographic analysis reveals that complex 1 exhibits a triple-decker Yb₃ sandwich structure with a ratio of H₂L:Yb = 1:1, while complex 2 exhibits a defect-dicubane Yb₄ core with a ratio of H₂L:Yb = 1:2. The NIR luminescence of complexes 1 and 2 have been investigated and discussed.     

Synthesis and Structural Characterization of Triorganotin(IV) Derivatives with 2,2′-Thiodiglycolic Acid and 3,3′-Thiodipropionic Acid

The synthesis and structural characterization of four novel triorganotin(IV) complexes, {(R₃Sn)₂[C₂H₄S(COO)₂]} _n (R = Me: 1), {(R₃Sn)₄[C₂H₄S(COO)₂]₂} _n (R = nBu: 2), {(R₃Sn)₂[C₄H₈S(COO)₂]} _n (R = Me: 3; nBu: 4) were obtained by the reaction of 2,2′-thiodiglycolic acid, 3,3′-thiodipropionic acid and the corresponding R₃SnCl (R = Me, nBu) with potassium hydroxide in methanol. All the complexes were characterized by elemental analysis, Fourier transform infrared and nuclear magnetic resonance (¹H, ¹³C, ¹¹⁹Sn) spectroscopies, X-ray crystallography and thermogravimetric analyses. The crystal structures show that 1 has 2D network structure in which 2,2′-thiodiglycolic acid acts as a tetradentate ligand coordinating to the trimethyltin(IV) ions. Complexes 2, 3, and 4 are 3D metal-organic framework structures in which the deprotoned acids act as a tetradentate ligand afforded by four oxygen atoms.     

Substitution of CO Ligand by P(OPh)3 in Radical Cations of the Cymantrene Family: Relationships of Substitution Rates to E1/2 Values and Carbonyl IR Frequencies

A series of piano-stool complexes of the cymantrene family (cymantrene = Mn(η⁵-C₅H₅)(CO)₃, 1) undergoes facile replacement of a carbonyl ligand by P(OPh)₃ when oxidized by one-electron in CH₂Cl₂/[NBu₄][B(C₆F₅)₄]. Data on the previously characterized complexes 1, Mn(η⁵-C₅H₄NH₂)(CO)₃ (3) and Mn(η⁵-C₅Me₅)(CO)₃ (6) have been supplemented by cyclic voltammetry (CV) and IR spectroscopy on Mn(η⁵-C₅H₄Me)(CO)₃ (2), Mn(η⁵-C₅H₄I)(CO)₃ (4), and Mn(η⁵-C₅H₄C(O)H)(CO)₃ (5). The substitution rates, determined by digital simulations of CV scans, ranged from 4 M^?1 s^?1 for 6 ⁺ to 3 × 10⁵ M^?1 s^?1 for 5 ⁺. In general, a more strongly donating cyclopentadienyl substituent slows down the CO substitution rate. For mono-cyclopentadienyl substituted complexes, the logarithm of k_sub is shown to increase linearly with either the weighted average of the CO stretching frequencies or the E_1/2 value of the redox process. An exception to this generalization is the amine-substituted complex 3, for which the CO-substitution rate is higher than predicted by its E_1/2 potential. The substitution rate of the pentamethylated Cp complex 6 ⁺ is slowed by about an order of magnitude owing to steric effects. The efficacy of this method to predict the CO-substitution rate of a cymantrene-tagged molecule was tested with a cymamtrene-derivatized diarylethene complex, 7. The measured P(OPh)₃-for-CO substitution rate of 3.7 × 10² M^?1 s^?1 for 7 ⁺ was very close to that predicted by the E_1/2 value of 7. A ligand electronic parameter, E_L, of 0.62 was determined for the triphenylphosphite ligand. These studies build on the previous CO substitution-rate analyses by Sweigart and others.     

Two New Luminescent Cadmium Thiolato-carboxylates with 2,2′-Bipyridine

Two new cadmium thiolato-carboxylate complexes, [Cd₂(mba)₂(2,2′-bpy)₂] (1), [Cd₂(dtba)₂(2,2′-bpy)₄]·4H₂O (2) (H₂mba = 2-mercaptobenzoic acid, H₂dtba = 2,2′-dithiodibenzoic acid, 2,2′-bpy = 2,2′-bipyridine) were obtained by reacting Cd(II) salts and the ligands of H₂mba and 2,2′-bpy, and were characterized by the single-crystal X-ray diffraction, IR, 2D-COS IR, solid UV, TG and XRD. In complex 2, the H₂dtba ligand came from the in situ S–S function reaction of H₂mba under the hydrothermal conditions. Complexes 1 and 2 are both 1D chains, but the difference lies in the linkage of the ligands. The 3D super-molecular frameworks of 1 and 2 are produced by π–π stacking interaction between the 2,2′-bpy ligands and the hydrogen bonds of O–H…O with ths-type and dia-type topology, respectively. The fluorescent emissions are observed in 1 and 2 with λ _em = 533 nm and λ _em = 436 nm, due to the ligand-to-metal charge transfer (LMCT) and π* → π transitions, respectively.     

A Strategy for Preparing Star Polymers Containing Metal–Metal Bonds Along the Polymeric Arms Using Click Chemistry

The [(η⁵-C₅H₄(CH₂)₃N₃)Mo(CO)₃]₂ dimer (3) was prepared and used to determine if the Huisgen cycloaddition reaction could be used to synthesize high molecular weight star polymers with metal–metal bonds in the arms. Several different click catalysts were examined. Cp*Ru(PPh₃)₂Cl (Cp* = η⁵-C₅(CH₃)₅) was previously shown to catalyze the formation of metal–metal bond-containing polymers using click chemistry; however, this catalyst underwent a Staudinger reaction with dimer 3 when a model coupling reaction was attempted with phenylacetylene. In order to avoid the Staudinger reaction, Cp*Ru(COD)Cl was used as the catalyst in the reaction of 3 with phenylacetylene, and coupling was observed after 14 h. Synthesis of a star polymer was attempted with 3 and 1,3,5-triethynylbenzene. Instead of coupling, Cp*Ru(COD)Cl reacted with the 1,3,5-triethynylbenzene. A third catalyst, Cu(IMes)Cl (IMes = 1,3-dimesityl-imidazol-2-ylidene) was used to couple 3 with 1,3,5-triethynylbenzene in 48 h. Both a high molecular weight polymer (M _n  = 77,000 g mol^?1) and a tripodal star core (M _n  = 1,800 g mol^?1) were successfully prepared with this catalyst.     

The Dipole Mediated Surface Chemistry of p-Benzoquinonemonoimine Zwitterions

This article reviews the surface adsorption of p-benzoquinonemonoimine zwitterions from the class of N-alkyldiaminoresorcinones (or 4,6-bis-dialkylaminobenzene-1,3-diones, i.e. C₆H₂(···NHR)₂(···O)₂), where R = H, R = C₂H₅, n-C₄H₉), on a variety of conducting surfaces. These small molecules with a large electrical dipole exhibit molecular orientation and packing on surfaces depending on the deposition methodology (from solution or from the vapor) as well as the substrate. What is very clear from the investigations of this class of molecules is that inter-molecular interaction is not simply driven by dipolar interactions alone, but frontier orbital symmetry as well. This is illustrated by the reversible adsorption of di-iodobenzene on molecular films of (6Z)-4-(butylamino)-6-(butyliminio)-3-oxocyclohexa-1,4-dien-1-olate C₆H₂(···NHR)₂(···O)₂ where R = n-C₄H₉, where it is clear that absorption is isomer specific.     

Metallopolymer Films Exhibiting Three-Color Electrochromism in the UV/Vis and Near-IR Region: Remarkable Utility of Trimetallic Clusters Bearing Thienyl Pendants and Their Mixed-Valent Charge Transfer Transitions

Novel oxo-centered, acetate-bridged trinuclear ruthenium clusters functionalized with two pyridine ligands with thienyl substituents, [Ru₃O(CH₃COO)₆(CO)(L1)₂] (1) and [Ru₃O(CH₃COO)₆(CO)(L2)₂] (2), where L1 = 4-(2-thienyl)pyridine and L2 = 4-(2,2′-bithienyl)pyridine, have been synthesized and characterized. The molecular structure of 2 has been determined by single-crystal X-ray diffraction. One-electron oxidation of 2 with silver(I) cation has led to the isolation of a CO-dissociated product, [Ru₃O(CH₃COO)₆(H₂O)(L2)₂]PF₆ (3·PF ₆ ), and subsequent reaction with 4-dimethylaminopyridine (dmap) gave [Ru₃O(CH₃COO)₆(dmap)(L2)₂]PF₆ (4·PF ₆ ). Linear metallopolymers containing the {Ru₃O(CH₃COO)₆} groups have been deposited onto indium-tin oxide surface via oxidative electropolymerization of 2, 3·PF ₆ , and 4·PF ₆ . These metallopolymer thin films exhibit three-color electrochromism in the UV/Vis and near-IR region associated with the Ru₃ ^II,III,III, Ru₃ ^III,III,III, and Ru₃ ^III,III,IV oxidation states.     

A Series of Luminescent Lanthanide–Organic Complexes Constructed from In Situ Generated Dithiobenzoic Acid

Two types of lanthanide thiolato-carboxylate complexes, [Type I: [Yb(dtba) (Hdtba)] _n (1), Type II: [Ln(dtba)_1.5(biim)] _n (Ln = Pr (2a), Nd (2b), Sm (2c), Eu (2d), Gd (2e), Tb (2f), Dy (2g), H₂dtba = 2,2′-dithiodibenzoic acid, bimm = diimidazole)] have been obtained by hydrothermal method and characterized by the single-crystal X-ray diffraction, IR, 2D-COS IR, TG and the luminescence analysis. The H₂dtba ligand came from the in situ S–S function reaction of 2-mercaptobenzoic acid (H₂mba) under the hydrothermal condition. Complex 1 is a 2D bamboo-like sqr-topology layered structure, and the 3D (4, 4, 6)-connected supramolecular frameworks is produced by the hydrogen bonds of O–H···O. Complexes of type II (from 2a to 2g) are isostructural and they are assigned to 1D rope-like chains by introducing the chelating ligand of diimidazole. These 1D rope-like chains are further linked by N–H···O hydrogen bonds into a 3D supramolecular framework with CdSO₄-type topology. Photoluminescence studies reveal that complexes 2b, 2c, 2d, 2f, 2g exhibit strong lanthanide characteristic emission bands in the solid state at room temperature.     

Salen Type Sandwich Triple-Decker Tri- and Di-nuclear Lanthanide Complexes

Four N,N′-bis(salicylidene)-1,2-(phenylene-ediamine) (H₂L) trinuclear lanthanide complexes, namely, [Ln₃L₃(CH₃OH)₂(NO₃)₃]·(CH₂Cl₂)·(CH₃OH)·(H₂O)₂ [Ln = Tb (1), Ho (2), Er (3) and Lu (4)], have been isolated by the reactions of H₂L and Ln(NO₃)₃·6H₂O. And one N,N′-bis(salicylidene)-1,2-(phenylene-ediamine) dinuclear neodymium complex [Nd₂L₃(CH₃OH)] (5) has been harvested from the reaction of H₂L with Nd(OAc)₃·4H₂O. X-ray crystallographic analysis reveals that complexes 1?4 are of triple-decker trinuclear sandwich structure, while complex 5 is of a triple-decker dinuclear sandwich structure, expanding upon the recent reports of the multinuclear pure lanthanide complexes.     

Uranyl Coordination Polymers Incorporating η5-Cyclopentadienyliron-Functionalized η6-Phthalate Metalloligands: Syntheses,Structures and Photophysical Properties

The reaction of two η⁵-cyclopentadienyliron(II)-functionalized terephthalate and phthalate metalloligands, namely [(η⁵-C₅H₅)Fe^II(η⁶-1,4-HO₂CC₆H₄CO₂H)][(η⁵-C₅H₅)Fe^II(η⁶-1,4-HO₂CC₆H₄CO₂)][PF₆] and [(η⁵-C₅H₅)Fe^II(η⁶-1,2-HO₂CC₆H₄CO₂H)][(η⁵-C₅H₅)Fe^II(η⁶-1,2-HO₂CC₆H₄CO₂)][PF₆]—hereafter [H₂ CpFeTP][HCpFeTP][PF₆] and [H₂ CpFeP][HCpFeP][PF₆], respectively—with [UO₂(NO₃)₂]·6H₂O under hydrothermal conditions yielded four new coordination polymers; (1) [(UO₂)F(HCpFeTP)(PO₄H₂)]·2H₂O, (2) [(UO₂)₂(CpFeTP)₄]·5H₂O, (3) [(UO₂)₂F₃(H₂O)(CpFeP)], and (4) [H₂ CpFeP][UO₂F₃]. The use of metalloligands has proven to be a viable route towards the incorporation of a secondary metal center into uranyl bearing materials. Depending upon the protonation state, the iron sandwich metalloligands may vary from zwitterionic neutral or monoanionic coordinating species as observed in compounds 1–3, or a positively charged species that hydrogen bonds with anionic [UO₂F₃]^? chains as observed in 4. Further, the hydrolysis of the charge balancing PF₆ ^? anion increases the diversity of UO₂ ²⁺ coordinating species by contributing both F^? and PO₄ ^3? anions (1, 3, 4). The luminescent properties of 1–4 were also studied and revealed the absence of uranyl emission, suggestive of a possible energy transfer from the uranyl cation to the iron(II) metal center.     

Polycatenated Bilayer Structure Containing Honeycomb-like 63 Layers

A new luminescent Zn(II) compound, [Zn₂(IN)₃(bpy)_0.5(CH₃COO)]·2(DMA) (1, IN = isonicotinate, bpy = 4,4′-bipyridine, DMA = N,N-dimethylacetamide), was synthesized under solvothermal condition and structurally characterized by single crystal X-ray diffraction. Compound 1 features a (3,4)-connected bilayer structure with honeycomb-like 6³ layers and bpy pillars. Each individual bilayer is catenated with two adjacent bilayers, giving rise to a rare 2D + 2D → 3D polycatenation motif.     

A Bimetallic Chain Based on [Mo(CN)8]3− and Er3+ Ions as Building Blocks: Synthesis and Magnetic Properties

A novel bimetallic 4d-4f complex, [Er^III(DMF)₄(H₂O)₂][Mo^V(CN)₈]·i-C₃H₇OH·4H₂O (1) (DMF = N,N′-dimethylformamide), has been synthesized and structurally characterized. The crystalline analysis shows that the build up of 1D zigzag-like chains produces complex 1, which is the first structurally characterized example of 1D structure based on the [Mo(CN)₈]^3? and Er³⁺ ions as building blocks. Complex 1 crystallizes in monoclinic system of space group P2₁/n, with a = 12.031(6), b = 16.027(7), c = 20.263(9) Å, β = 105.711(6)º and Z = 4. Magnetic measurements confirm that 1 presents probably a ferromagnetic interaction between the Mo^V and Er^III ions.     

Three New Coordination Polymers Constructed from Mixed Ligands: Syntheses,Luminescence and Magnetism

Three new coordination polymers, namely, {[Cd(H₂bptc)(IP)(H₂O)]·2H₂O} _n (1), {[Mn₂(IP)₂(dstc)]·6H₂O} _n (2) and {[Zn₂(IP)₂(dstc)]·3H₂O} _n (3) (IP = 1H-imidazo[4,5-f][1,10]-phenanthroline, H₄bptc = 3,3′,4,4′-benzophenonetetracarboxylic acid, and H₄dstc = 3,3′,4,4′-diphenylsulfonetetracarboxylic acid) have rationally designed and characterized by single crystal X-ray diffraction. Polymer 1 shows a 1D ribbon-like structure. Although compounds 2 and 3 feature 2D grid networks, the coordinative modes of dstc ligand and the arrangements of IP ligand are very different. Furthermore, the luminescence properties for 1 and 3, as well as the magnetism of 2 are explored in detail.     

Synthesis,Crystal Structures,Luminescence, Biological and Catalytic Properties of Two d10 Metal-Organic Coordination Polymers Constructed from Mixed Ligands

Two d¹⁰ metal-organic coordination polymers, [Cd₂(4-cpa)₄(bmip)₂]_n (1) and [Zn(4-cpa)₂(4,4′-bpy)]_n (2), [4-cpa = 4-chlorophenylacetate, bmip = 1,3-bis(2-methylimidazoly)propane, 4,4′-bpy = 4,4′-bipyridine], were hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicated that both 1 and 2 display analogous wave-like infinite chain structures. The two coordination polymers are further extended into 3D supramolecular structures through π···π stacking interactions and C–H···O hydrogen bonds for 1 and π···π stacking interactions, C–H···π stacking interactions and C–H···O hydrogen bonds for 2. Both 1 and 2 emit the intense blue luminescence at room temperature. The 4-Hcpa ligand and complexes 1 and 2 have been screened for their herbicidal activities against Brassica napus L. and Echinochloa crusgalli L. The results are compared with the activity of quizalofop-P-ethyl. Both compounds exhibit high catalytic properties on degradation of methyl orange in Fenton-like process.     

Construction of Two New Metal–Organic Frameworks from Pamoic Acid and N-Containing Auxiliary Ligands

Two new metal–organic frameworks; namely, [Cd₂(pam)₂(bpe)_1.5(DMF)₂(H₂O)] _n ·2n(DMF) (1) and [Cd(pam)(bix)] _n (2) (H₂pam = pamoic acid, bpe = 1,2-di(4-pyridyl)ethylene, bix = 4,4′-bis(imidazol-1-ylmethyl)benzene, DMF = N,N′-dimethylformamide), were solvothermally synthesized via varying the auxiliary ligand. Single crystal X-ray diffraction analysis reveals that compound 1 shows a 2D→3D polythreaded motif based on (3,4)-connected 2D sheets, while compound 2 features a 4-connected sql tetragonal plane net, which further extended into a 3D supramolecular framework through intermolecular CH···π interactions. In addition, the luminescent and thermal stabilities properties of these two compounds were investigated.     

Urothermal Synthesis of a Photoluminescent Coordination Polymer with Rutile Topology

A new coordination polymer [Cd₃(btc)₂(e-urea)₄]^.(e-urea)₂ (1; btc = 1,3,5-benzenetricarboxylate; e-urea = ethyleneurea) has been urothermally synthesized using ethyleneurea hemihydrate as the solvent and exhibits (3,6)-connected rutile (rtl) topology. The structure of 1 consists of trinuclear Cd units and the btc linkers. Species 1 features a non-interpenetrating three-dimensional open framework with channels filled by the e-urea additives and guest molecules. The thermogravimetric behavior and photoluminescent property of 1 were studied.