Synthesis,Crystal Structure and Magnetism Characterization of Two Coordination Polymers based on Ni(2‐mpac)2(H2O)2 as Molecular Building Block

Taking Ni(2‐mpac)₂(H₂O)₂ as molecular building block, two novel coordination polymers with the formula of [Ni(2‐mpac)₂(4,4′‐bpy)·(4,4′‐bpy)]_n ( 1 ) and [Ni(2‐mpac)₂(py)·4H₂O]_n ( 2 ) (2‐mpac = 5‐methyl‐2‐pyrazinecarboxylic acid; 4,4′‐bpy = 4,4′‐bipyridine; py = pyrazine) have been synthesized and structurally characterized by X‐ray single crystal diffraction method. In addition, elemental analysis, IR and magnetism characterization are presented.     

Synthesis and photophysical properties of novel amphiphilic ruthenium (II) complexes containing 4,4′‐dialkylaminomethyl‐2,2′‐bipyridyl ligands

The synthesis of a number of new 2,2′‐bipyridine ligands functionalized with bulky amino side groups is reported. Three homoleptic polypyridyl ruthenium (II) complexes, [Ru(L)₃]²⁺ 2(PF₆^?), where L is 4,4′‐dioctylaminomethyl‐2,2′‐bipyridine (Ru4a), 4,4′‐didodecylaminomethyl‐2,2′‐bipyridine (Ru4b) and 4,4′‐dioctadodecylaminomethyl‐2,2′‐bipyridine (Ru4c), have been synthesized. These compounds were characterized and their photophysical properties examined. The electronic spectra of three complexes show pyridyl π → π* transitions in the UV region and metal‐to‐ligand charge transfer bands in the visible region. Copyright © 2005 John Wiley & Sons, Ltd.     

Syntheses,Crystal Structures and Luminescent Properties of Three Inorganic‐Organic Hybrid Frameworks Constructed from 4,5‐Imidazoledicarboxylate

Three inorganic‐organic hybrid frameworks [Mn(HIMDC)(4,4′‐bipyo)_0.5(H₂O)]_n (1) , [Cd(H₂IMDC)₂(2,2′‐bipyo)] (2) and [Ca(HIMDC)(H₂O)₂·H₂O]_n (3) (H₃IMDC = 4,5‐imidazoledicarboxylate; 4,4′‐bipyo = 4,4′‐bipyridine‐N,N′‐dioxide; 2,2′‐bipyo= 2,2′‐bipyridine‐N,N′‐dioxide) have been hydrothermally synthesized and characterized by the elemental analyses, IR spectra, TG analysis and the single crystal diffraction. Both compounds 1 and 3 exhibit 2D layers while 2 is a monomer. It is noteworthy that compound 2 exhibits strong fluorescent emission in the solid state at room temperature.     

Cadmium(II) Complexes with a Bulky Anthracene‐based Carboxylate Ligand: Syntheses,Crystal Structures,and Luminescent Properties

To explore the coordination possibilities of anthracene‐based ligands, three cadmium(ιι) complexes with anthracene‐9‐carboxylate ( L ) and relevant auxiliary chelating or bridging ligands were synthesized and characterized: Cd₂( L )₄(2bpy)₂(μ‐H₂O) ( 1 ), Cd₂( L )₄(phen)₂(μ‐H₂O) ( 2 ), and {[Cd₃( L )₆(4bpy)]}_∞ ( 3 ) (2bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, and 4bpy = 4,4′‐bipyridine). Structural analyses show that complexes 1 and 2 both take dinuclear structures by incorporating the chelating 2bpy or phen ligand, which are further interlinked by intermolecular hydrogen‐bonding, π ··· π stacking, and/or C–H ··· π supramolecular interactions to generate higher‐dimensional supramolecular frameworks. Complex 3 has a one‐dimensional (1D) ribbon‐like structure, which is further assembled into a two‐dimensional (2D) layer, and a three‐dimensional (3D) framework by the co‐effects of interchain C–H ··· O hydrogen‐bonding and C–H ··· π supramolecular interactions. Moreover, the luminescent properties of these complexes were further investigated in detail.     

Solvothermal Synthesis and Crystal Structures of Two Manganese Complexes [Mn(II)(acac−)2(4,4′‐bipy)]n (bipy=4,4′‐bipyridine) and [Mn(III)(acac−)3]·4CO(NH2)2

Two special manganese complexes [Mn(II)(acac^?)₂(4,4′‐bipy)]_n (bipy=4,4′‐bipyridine) (complex 1 ) and [Mn(III)(acac^?)₃]·4CO(NH₂)₂ (acacH=acetylacetone) (complex 2 ) were synthesized in the same strategy by solvothermal method. Single crystal X‐ray diffraction revealed the complex 1 consists of one‐dimensional infinite coordination chain, with the manganese centers bridged by 4,4′‐bipy. And free carbamides of complex 2 connect with each other through the hydrogen bonds to form a 14‐membered carbamide ring and a zig‐zag plane. Both enantiomers of Mn(III)(acac^?)₃ exist in the structure, forming a racemate. Furthermore, these enantiomers and those zig‐zag planes are linked with hydrogen bonds to form an unique spatial network.     

Electrocrystallization of Tetra‐ and Hexa‐coordinated Silver(II) Compounds Based on 4,4′‐Dimethyl‐2,2′‐Bipyridine Ligand – Single Crystal Structures and Magnetic Studies

In this paper we report on the potential dependent electrocrystallization of [Ag(4,4′‐dimethyl‐2,2′‐bipyridine)₂(NO₃)₂] ( 1 ) and Ag(4,4′‐dimethyl‐2,2′‐bipyridine)(NO₃)₂ ( 2 ) from the same electrolytic bath. Thus it has been shown for the first time that the coordination number of silver ion to ligands can be tuned by the electrocrystallization potential. The single crystal structure analysis [ 1 : C2/c, a = 18.6308(15), b = 14.5708(12), c = 11.5867(10) Å, β = 126.5910(10)°, Z = 4, R = 3.9 %] [ 2 : P2₁/c, a = 8.5865(11) b = 11.0157(14) c = 16.4554(10) Å, β = 111.102(10), Z = 4 , R = 3.5 %] show divalent silver to be in an approximately square planar surrounding. Both complexes are paramagnetic following Curie's law with magnetic moments of 1.86 μ_B and 1.72 μ_B respectively.     

A 1,2,4‐Triazole‐based Polynuclear Mixed‐valence MnIIMnIII Complex: Synthesis,Characterization, and Magnetic Property

A mixed‐valence Mn complex {[Mn^IIMn^III(HL)₂(4,4′‐bpy)(H₂O)₂] · (ClO₄)(DMF)₃(4,4′‐bpy)_0.5}_n ( 1 ) [H₂L = 3‐(2‐phenol)‐5‐(pyridin‐2‐yl)‐1,2,4‐triazole] was synthesized and characterized by X‐ray single‐crystal structure analysis and magnetic susceptibility. Single‐crystal X‐ray analysis revealed that complex 1 has a dinuclear core, in which adjacent central Mn^III atoms are linked by 4,4′‐bipyridine to form an infinite one‐dimensional (1D) molecular configuration. According to the Mn surrounding bond lengths and bond valence sum (BVS) calculations, we demonstrated that the Mn atom coordinated to the pyridine N atoms is in the +2 oxidation state, while another Mn atom coordinated to the phenolic oxygen atoms is in the +3 oxidation state. Magnetic susceptibility data of the complex 1 indicate that the ferromagnetic interaction dominates in this complex.     

Synthesis and Crystal Structures of Manganese(II) and ­Cobalt(II) Complexes with 2, 6‐Dimethoxybenzoic Acid and Additional N‐Donor Ligands

Three coordination compounds [Mn₃(dmb)₆(H₂O)₄(4, 4′‐bpy)₃(EtOH)]_n ( 1 ) and [M(dmb)₂(pyz)₂ (H₂O)₂] [M^II = Co ( 2 ), Mn ( 3 )] (Hdmb = 2, 6‐dimethoxybenzoic acid, 4, 4′‐bpy = 4, 4′‐bipyridine, pyz = pyrazine) were synthesized and characterized by single‐crystal X‐ray diffraction analysis. Compound 1 consists of infinite 1D polymeric chains, in which the metal entities are bridged by 4, 4′‐bpy ligands. There are four crystallographically independent Mn^II atoms in the linear chain with different coordination modes, which is only scarcely reported for linear polymers. The isostructural crystals of 2 and 3 are composed of neutral mononuclear complexes. In crystal the complexes are combined into chains by intermolecular O–H ··· N hydrogen bonds and π–π interactions between antiparallel pyrazine molecules.     

Crystal Structure and Luminescence of a Europium Coordination Polymer {[Eu(p-MOBA)_3·2H_2O]·0.5H_2O· 0.5(4,4′-bipy)}_∞

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Supramolecular Stuctures from Mononuclear,Binuclear and 2D Net of Copper(II) Complexes with 6‐Hydroxypicolinic Acid

First examples of transition metal complexes with HpicOH [Cu(picOH)₂(H₂O)₂] ( 1 ), [Cu(picO)(2,2′‐bpy)]·2H₂O ( 2 ), [Cu(picO)(4,4′‐bpy)_0.5(H₂O)]_n ( 3 ), and [Cu(picO)(bpe)_0.5(H₂O)]_n ( 4 ) (HpicOH = 6‐hydroxy‐picolinic acid; 2,2′‐bpy = 2,2′‐bipyridine; 4,4′‐bpy = 4,4′‐bipyridine; bpe = 1,2‐bis(4‐pyridyl)ethane) have been synthesized and characterized by single‐crystal X‐ray diffraction. The results show that HpicOH ligand can be in the enol or ketonic form, and adopts different coordination modes under different pH value of the reaction mixture. In complex 1 , HpicOH ligand is in the enol form and adopts a bidentate mode. While in complexes 2 – 4 , as the pH rises, HpicOH ligand becomes in the ketonic form and adopts a tridentate mode. The coordination modes in complexes 1 – 4 have not been reported before. Because of the introduction of the terminal ligands 2,2′‐bpy, complex 2 is of binuclear species; whereas in complexes 3 and 4 , picO ligands together with bridging ligands 4,4′‐bpy and bpe connect Cu^II ions to form 2D nets with (12³)₂(12)₃ topology.     

Synthesis and Characterization of a Novel Binuclear Cobalt(II) Complex with Discrete Water Clusters (H2O)8

A new octameric water cluster was observed in the complex Co₂(dptc)(bipy)₂(H₂O)₆ · 4H₂O ( 1 ) (H₄dptc = diphenyl‐3,3′,4,4′‐tetracarboxylic acid; bipy = 2,2′‐bipyridine), which was characterized by single‐crystal X‐ray diffraction, elemental analysis and IR spectroscopy. The centrosymmetric octamer consists of a water hexamer in the chair form and two water molecules and brings to light a novel mode of the cooperative association of water molecules. Those complex units are connected into a 2D infinite layer framework through hydrogen bonding. Consequently, the 2D layers are further aggregated by hydrogen bonding with octameric subunits and π ··· π stacking interactions to form a 3D supramolecular architecture.     

Diverse Coordinative Functions of 4,4′‐Bipyridine Generating Abundant Weak Interactions and Novel Fluorescent Property in Cadmium(II)‐4‐sulfobenzoate Polymer

The cadmium(II) 4‐sulfobenzoate complex with 4,4′‐bipyridine, {[Cd₂(4,4′‐bipy)₄(4‐sb)₂(H₂O)₃] · 4H₂O}_n, has been synthesized and characterized by elemental analysis, IR, DTA‐TG, fluorescence analysis, powder X‐ray analysis, and single‐crystal X‐ray structural determination. Structural analysis showed that the complex contains two Cd atoms in an unsymmetrical unit. The Cd1 atom displays a seven‐coordinated geometry, which is a capped anti‐trigonal prismatic structure, whereas the Cd2 atom has an octahedral coordination. The 4,4′‐bipyridine ligands in the complex have three coordination behaviors, i.e., monodentate, dimeric linker, and polymeric bridge, which is the first example showing three coordinative functions for 4,4′‐bipyridine ligands in one complex. Moreover, three coordinative functions of 4,4′‐bipyridine ligands in this polymer lead to abundant weak interactions and novel fluorescent properties, which is benefit for design and preparation of functional materials in specific usage.     

Two New Solvent‐modulated Zinc(II) Metal‐Organic Hybrid Materials based on Rigid Tripodal Carboxylate Ligand and 2,2′‐Bipy Co‐ligand: Crystal Structures and Luminescent Properties

The zinc(II) coordination polymers [Zn(Htatb)(2,2′‐bipy) · (NMP) · H₂O] ( 1 ) and [Zn₃(tatb)₂(2,2′‐bipy)₃ · H₂O] ( 2 ) (H₃tatb = 4,4′,4′′‐s‐triazine‐2,4,6‐triyl‐tribenzoic acid; 2,2′‐bipy = 2,2′‐bipyridyl, NMP = N‐methyl‐2‐pyrrolidon), were synthesized hydrothermally, and characterized by infrared spectroscopy (IR), powder X‐ray diffraction (PXRD), and single‐crystal X‐ray diffraction. Both compounds 1 and 2 possess expectant low dimensional coordination structures, which further connected into interesting 3D networks by hydrogen bond and strong π–π interactions. Moreover, the thermal stabilities and fluorescent properties of 1 and 2 were investigated.     

Synthesis,Characterization, and Luminescence of Two New Zinc(II) Coordination Polymers Constructed by 5‐(4‐Carboxybenzyloxy)Isophthalic Acid Ligand

Two coordination polymers, namely Zn(HL)(4,4′‐bpy)_1.5 ( 1 ), [Zn₃(L)₂(BIMB)₂] · 5H₂O ( 2 ) [H₃L = 5‐(4‐carboxybenzyloxy)isophthalic acid, 4,4′‐bpy = 4,4′‐bipyridine, BIMB = 1,4‐bis(1H‐imidazol‐1‐yl)benzene] were synthesized under hydrothermal conditions. Their structures are determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, and thermogravimetric (TG) analyses. Complex 1 features a 2D 4‐connected network. Complex 2 is a 3D twofold interpenetrating (3,4,6)‐connected net. In addition, the luminescent properties for 1 and 2 were studied in the solid state at room temperature.     

New Examples of Metal Coordination Architectures of 3,3′,4,4′‐Biphenyltetracarboxylic Acid – Syntheses,Crystal Structures,and Physical Properties

Four new metal‐organic frameworks [Cu₂(2,2′‐bipy)₂(ox)(H₂O)₂]·(H₂bptc) ( 1 ), [Cu(bptc)_0.5(phen)(H₂O)]·H₂O ( 2 ), Co₂(bptc)(bmb)_1.5 ( 3 ) and [Cd₂(bptc) (bmb)]·3H₂O ( 4 ) (H₄bptc = 3,3′,4,4′‐biphenyltetracarboxylic acid, ox = oxalate, phen = 1,10‐phenanthroline, 2,2′‐bipy = 2,2′‐bipyridine and bmb = 4,4′‐bis((1H‐imidazol‐1‐yl)methyl)biphenyl), were obtained by reactions of the corresponding metal salts with H₄bptc and N‐containing auxiliary ligands and their structures were determined by single‐crystal X‐ray diffraction. The results reveal that 1 has a 0‐D structure consisting of discrete ionic entities, while 2 features a 1‐D ladder structure. Additionally, there exist π‐π stacking and intermolecular hydrogen‐bonding interactions in 1 and 2 , respectively, forming 3‐D supramolecular structures. In 3 ‐ 4 , undulating 2‐D metal‐bptc layer structures are formed with two different coordination modes of bptc carboxylate groups, respectively, which are further extended by bmb into 3‐D structures. Magnetic properties of 1 and 3 have been studied. The photoluminescence property of 4 has also been investigated. Moreover, nonlinear optical measurements showed that 4 displayed a second‐harmonic‐generation (SHG) response of 0.7 times of that for urea.     

One-Pot Hydrothermal Synthesis of Two New Copper（Ⅱ） Complexes with 4-Carboxyphenoxy Acetic Acid

The one-pot hydrothermal reaction of CuCl2 with H2CPOA and 4,4＇-bpy results in two new coordination polymers, [Cu（CPOA）（4,4＇-bpy）（H2O）2]·1.5H2O （1） and [Cu2（HCPOA）4（4,4＇-bpy）4] （2） （H2CPOA=4-carboxyphenoxy acetic acid, 4,4＇-bpy=4,4＇-bipyridine） since CPOA^2- anions reach equilibrium with HCPOA^- anions in the reaction system. The crystal structure of 1 shows a triple interpenetration CdSO4-like net with 1D channel, in which lattice water molecules are located. Complex 2 is a ladder-like 1D double chain structure assembled through coordination bonds and O—H…N hydrogen bonds.     

Synthesis, Characterization, Spectroscopic and Electrochemical Properties of New Mono- and Binuclear Copper（Ⅰ） Complexes with Substituted 2,2′-Bipyridine

The mono- and binuclear Cu(Ⅰ) complexes with substituted 2,2′-bipyridine and iodide ligands, [CuL2]BF4(L=4-methoxycarbonyl-6-(4-methylphenyl)-2,2′-bipyridine (a), 6-(4-hydroxymethylphenyl)-2,2′-bipyridine (b) and 6-(4-methoxylphenyl)-2,2′-bipyridine (c)) and [Cu2(μ-I)2L2] were prepared, and the crystal structures of the complexes were obtained from signal-crystal X-ray diffractional analysis. The spectroscopic properties of the complexes in dichloromethane are dominated by low energy MLCT bands from 360 to 650 nrn. The electrochemical studies of mononuclear complexes reveal that the complexes have stable copper(Ⅰ) state.     

4,4’－二(磷酸二甲酯甲基)联苯连接的具有互穿结构的二维锰(II)配位聚合物的合成与结构研究

在常规条件下,合成了具有新颖结构的配位聚合物[Mn(bdpbp)2(NO3)2]n (1) [bdpbp =4,4’-二(磷酸二甲酯甲基)联苯]。配合物1由单晶x-射线衍射确定结构,并用元素分析、红外光谱、荧光光谱和热重进行了表征和性质研究。配合物1具有二维无限的网格状结构,形成双重互穿,并由弱的C-H···O氢键进一步连接成三维超分子网络。     

Syntheses and crystal structures of triorganotin (IV) derivatives with 2,2′‐bipyridine‐4,4′‐dicarboxylic acid

Four organotin complexes with 2,2′‐bipyridine‐4,4′‐dicarboxylic acid, H₂dcbp: (Ph₃n)₂(dcbp) 1 , [(PhCH₂)₃n]₂(dcbp) ⋅ 2CH₃OH 2 , [(Me₃Sn)₂(dcbp)]_n 3 , [(Bu₃Sn)₂(dcbp)]_n 4 have been synthesized. The complexes 1–4 were characterized by elemental, IR, ¹H, ¹³C, ¹¹⁹n NMR, and X‐ray crystallographic analyses. Crystal structures show that complex 1 is a monomer with one ligand coordinated to two triorganotin moieties, and a 1D infinite polymeric chain generates via intermolecular C H⋅⋅⋅N hydrogen bond; complex 2 is also a monomer and forms a 2D network by intermolecular O–H⋅⋅⋅O weak interaction; both of complexes 3 and 4 form 2D network structures where 2,2′‐bipyridine‐4,4′‐dicarboxylate acts as a tetradentate ligand coordinated to trimethyltin and tri‐n‐butyltin ions, respectively. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:19–28, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20506     

Crystal Structures and Photoluminescence Properties of Zinc(II) and Cadmium(II) Coordination Polymers with “Y”‐Shaped Ligands

Three Zn^II and Cd^II complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L₁)(2,2′‐bpy)₂(H₂O)] · 2H₂O ( 1 ), [Zn(L₁)(bpp)(H₂O)] ( 2 ), and [Cd(L₁)(H₂O)] · H₂O ( 3 ) [H₂L₁ = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H ··· O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.8²). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1 – 3 were also investigated.