trans‐(Cl)‐[Ru(5,5′‐diamide‐2,2′‐bipyridine)(CO)2Cl2]: Synthesis,Structure, and Photocatalytic CO2 Reduction Activity

A series of trans‐(Cl)‐[Ru(L)(CO)₂Cl₂]‐type complexes, in which the ligands L are 2,2′‐bipyridyl derivatives with amide groups at the 5,5′‐positions, are synthesized. The C‐connected amide group bound to the bipyridyl ligand through the carbonyl carbon atom is twisted with respect to the bipyridyl plane, whereas the N‐connected amide group is in the plane. DFT calculations reveal that the twisted structure of the C‐connected amide group raises the level of the LUMO, which results in a negative shift of the first reduction potential (E_p) of the ruthenium complex. The catalytic abilities for CO₂ reduction are evaluated in photoreactions (λ>400 nm) with the ruthenium complexes (the catalyst), [Ru(bpy)₃]²⁺ (bpy=2,2′‐bipyridine; the photosensitizer), and 1‐benzyl‐1,4‐dihydronicotinamide (the electron donor) in CO₂‐saturated N,N‐dimethylacetamide/water. The logarithm of the turnover frequency increases by shifting E_p a negative value until it reaches the reduction potential of the photosensitizer.     

Bis(2,2′‐bipyridine)(dicyanamido)­copper(II) tetrafluoroborate

In the title compound, [Cu(C₂N₃)(C₁₀H₈N₂)₂]BF₄, the Cu^II atom shows distorted trigonal‐bipyramidal geometry, with the dicyan­amido ligand in the equatorial plane. The two out‐of‐plane Cu—N bond lengths to bi­pyridine are 2.006 (3) and 1.998 (3) Å, whereas the in‐plane Cu—N distances are 2.142 (3) and 2.043 (3) Å to the bi­pyridine, and 2.015 (3) Å to the dicyan­amide.     

Synthesis and Crystal Structure of Manganese(II) Bipyridine Carboxylato Complexes: [(bipy)2MnII(μ‐C2H5CO2)2MnII(bipy)2](ClO4)2 and [MnII(ClCH2CO2)(H2O)(bipy)2]ClO4 · H2O (bipy = 2,2′‐bipyridine)

Two manganese(II) bipyridine carboxylate complexes, [(bipy)₂Mn^II(μ‐C₂H₅CO₂)₂Mn^II(bipy)₂}₂](ClO₄)₂ ( 1 ), and [Mn^II(ClCH₂CO₂)(H₂O)(bipy)₂]ClO₄ · H₂O ( 2 ) were prepared. 1 crystallizes in the triclinic space group P 1 with a = 8.604(3), b = 12.062(3), c = 13.471(3) Å, α = 112.47(2), β = 93.86(2), γ = 92.87(3)°, V = 1211.1(6) ų and Z = 1. In the dimeric, cationic complex with a crystallographic center of symmetry two 2,2′‐bipyridine molecules chelate each manganese atom. These two metal fragments are then bridged by two propionato groups in a syn‐anti conformation. The Mn…Mn distance is 4.653 Å. 2 crystallizes in the monoclinic space group P2₁/c with a = 9.042(1), b = 13.891(1), c = 21.022(3) Å, β = 102.00(1)°, V = 2569.3(5) ų and Z = 4. 2  is a monomeric cationic complex in which two bipyridine ligands chelate the manganese atom in a cis fashion. A chloroacetato and an aqua ligand complete the six‐coordination. Only in 2 is the intermolecular packing controlled by weak π‐stacking besides C–H…π contacts between the bipyridine ligands.     

Polymorphism of [Zn(2,2′‐bipy)(H2PO4)2]2

Two polymorphs of a zero‐dimensional (molecular) zinc phosphate with the formula [Zn(2,2′‐bipy)(H₂PO₄)₂]₂ have been synthesized by a mild hydrothermal route and their crystal structures were determined by single crystal X‐ray diffraction (triclinic, space group (No. 2), Z = 2, α‐form: a = 8.664(1), b = 8.849(2), c = 10.113(2) Å, α = 97.37(2)°, β = 100.54(2)°, γ = 100.98(2)°, V = 737.5(3) ų; β‐form: a = 7.5446(15), b = 10.450(2), c = 10.750(2) Å, α = 67.32(3)°, β = 81.67(3)°, γ = 69.29(3)°, V = 731.4(3) ų). Both structures consist of distorted trigonal‐bipyramidal ZnO₃N₂ units condensed with PO₂(OH)₂ tetrahedra through common vertices giving rise to dimers [Zn(2,2′‐bipy)(H₂PO₄)₂]₂. The structures are stabilized by extensive inter‐ and intramolecular hydrogen bond interactions. Both modifications display subtle differences in their packing originating from the hydrogen bond interactions as well as π…π interactions between the organic ligands.     

Luminescence characteristics and X‐ray crystal structure of [Cd(bipy)3][PF6]2 (bipy = 2,2′‐bipyridine)

The photoluminescence characteristics of the [Cd(bipy)₃][PF₆]₂ complex are reported. A moderately large quantum yield (φ) of 1.07 × 10^?2 is exhibited in acetonitrile solution at 298 K. Crystallography shows the dication to have a distorted octahedral geometry and the crystal structure to be stabilized by C? H···π and C? H···F interactions. Copyright © 2005 John Wiley & Sons, Ltd.     

The 3D Supramolecular Compound {[Cu2(L‐val)2(4,4′‐bipy)(H2O)2](NO3)2}n (L‐val = L‐valine anion, 4,4′‐bipy = 4,4′‐bipyridine)

{[Cu₂(L‐val)₂(4,4′‐bipy)(H₂O)₂](NO₃)₂}_n was synthesized and its crystal structure was determined by X‐ray diffraction. In the presence of 4,4′‐bipyridine, deprotoned L‐valine chelates Cu^II ions into coordination layers which were linked into a framework by hydrogen‐bonded chains resulting from nitrate anions and water molecules.     

4,4′‐Bis(2,2,2‐trifluoroethoxymethyl)‐2,2′‐bipyridine

As part of a homologous series of novel polyfluorinated bipyridyl (bpy) ligands, the title compound, C₁₆H₁₄F₆N₂O₂, contains the smallest fluorinated group, viz. CF₃. The molecule resides on a crystallographic inversion centre at the mid‐point of the pyridine C_ipso—C_ipso bond. Therefore, the bpy skeleton lies in an anti conformation to avoid repulsion between the two pyridyl N atoms. Weak intramolecular C—H...N and C—H...O interactions are observed, similar to those in related polyfluorinated bpy–metal complexes. A π–π interaction is observed between the bpy rings of adjacent molecules and this is probably a primary driving force in crystallization. Weak intermolecular C—H...N hydrogen bonding is present between one of the CF₃CH₂– methylene H atoms and a pyridyl N atom related by translation along the [010] direction, in addition to weak benzyl‐type C—H...F interactions to atoms of the terminal CF₃ group. It is of note that the O—CH₂CF₃ bond is almost perpendicular to the bpy plane.     

一个新颖的由Zn配合物修饰的Keggin型钴钨酸盐：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O

通过水热合成技术,一个新颖的基于Zn配合物修饰的Keggin型钴钨酸的有机-无机杂化化合物：[Zn(2,2’-bipy)3]3{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2 }.H2O已经被合成,化合物通过红外光谱、热重分析和单晶X-射线衍射进行了表征。单晶X-射线衍射的结果显示标题化合物是由一个单支撑的{[Zn(2,2’-bipy)2(H2O)]2 [HCoW12O40] 2}6-多阴离子,三个[Zn(2,2’-bipy)3]2+阳离子和一个水分子构成。有趣的是[Zn(1)(2,2’-bipy)3]2+阳离子通过氢键连接在一起形成螺旋链。另外标题化合物在空气中是稳定的,并且在室温下显示了强的荧光。     

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.     

4,4′‐Bipyridine‐1,1′‐diium acetylenedicarboxylate: a new member of the (H2bipy)[Cu(ox)2] (bipy is 4,4′‐bipyridine and ox is oxalate) family

4,4′‐Bipyridine‐1,1′‐diium (H₂bipy) acetylenedicarboxylate, C₁₀H₁₂N₂²⁺·C₄O₄²⁻, (1), is a new member of a family of related structures with similar unit‐cell parameters. The structures in this family reported previously [Chen et al. (2012). CrystEngComm, 14 , 6400–6403] are (H₂bipy)[Cu(ox)₂] (ox is oxalate), (2), (H₂bipy)[NaH(ox)₂], (3), and (H₂bipy)[H₂(ox)₂], (4). Compound (1) has a one‐dimensional structure, in which H₂bipy²⁺ cations and acetylenedicarboxylate (ADC²⁻) anions are linked through a typical supramolecular synthon, i.e.R₂²(7), and form linear `–cation–anion–' ribbons. Through an array of nonclassical C—H...O hydrogen bonds, adjacent ribbons interact to give two‐dimensional sheets. These sheets stack to form a layered structure viaπ–π interactions between the H₂bipy²⁺ cations of neighbouring layers. The supramolecular isostructurality of compounds (1)–(4) is ascribed to the synergistic effect of multiple interactions in these structures. The balanced strong and weak intermolecular interactions stabilizing this structure type include strong charge‐assisted N—H...O hydrogen bonds, C—H...O contacts and π–π interactions.     

Tuning the Excited—state Properties of Cyclometalated Platinum（Ⅱ）Complexes of 6—Pheny1—2,2’bipyridine by Ancillary Acetylide Ligand

A series of luminescent cyclometalated platinum(Ⅱ）complexes,(C^N^N)Pt(C≡CR)[HC^N^N=4-(4-tolyl)-6-phenyl-2,2’-bipyridine;R=4-chlorophenyl(1),phenyl(2) and 4-tolyl(3)],were synthesized,and their spectroscopic properties have been examined.These complexes are brightly emissive both in fluid solution and in the solid state,attributed to triplet metal-to-ligand charge transfer(^3MLCT)state.The excited state energy can be tuned by ancillary acetylide ligands.The emission lifetimes in dichloromethand solution at room temperature were up to 1.64 μs and the emission quantum yields were in the range of 0.03-0.15.     

Tetrakis(μ‐2,3‐dimethoxybenzoato)bis[(2,2′‐bipyridine)(2,3‐dimethoxybenzoato)lanthanum(III)]

The title compound, tetrakis(μ‐2,3‐di­methoxy­benzoato)‐κ⁴O:O′;κ⁶O,O′:O′‐bis[(2,2′‐bi­pyridine‐N,N′)(2,3‐di­methoxy­benzoato‐O,O′)lanthanum(III)], [La₂(2,3‐DMOBA)₆(2,2′‐bpy)₂], where 2,3‐DMOBA is 2,3‐di­methoxy­benzoate (C₉H₉O₄) and 2,2′‐bpy is 2,2′‐bi­pyridine (C₁₀H₈N₂), is a dimer with a centre of inversion between the La atoms bridged by four carboxyl­ate ligands. The central La atom is ennea‐coordinated and has a distorted monocapped square‐antiprism geometry.     

A chloro(2‐pyridinecarboxaldehyde)(2,2′:6′,2′′‐ter­pyridine)­ruthenium(II) complex

The aldehyde moiety in the title complex, chloro(2‐pyridinecarboxaldehyde‐N,O)(2,2′:6′,2′′‐terpyridine‐κ³N)ruthenium(II)–chloro­(2‐pyridine­carboxyl­ic acid‐N,O)(2,2′:6′,2′′‐ter­pyridine‐κ³N)­ruthenium(II)–perchlorate–chloro­form–water (1.8/0.2/2/1/1), [RuCl­(C₆H₅NO)­(C₁₅H₁₁N₃)]_1.8[RuCl­(C₆H₅­NO₂)(C₁₅H₁₁N₃)]_0.2­(ClO₄)₂·­CHCl₃·­H₂O, is a structural model of substrate coordination to a transfer hydrogenation catalyst. The title complex features two independent Ru^II complex cations that display very similar distorted octahedral coordination provided by the three N atoms of the 2,2′:6′,2′′‐ter­pyridine ligand, the N and O atoms of the 2‐pyridine­carbox­aldehyde (pyCHO) ligand and a chloride ligand. One of the cation sites is disordered such that the aldehyde group is replaced by a 20 (1)% contribution from a carboxyl­ic acid group (aldehyde H replaced by carboxyl O—H). Notable dimensions in the non‐disordered complex cation are Ru—N 2.034 (2) Å and Ru—O 2.079 (2) Å to the pyCHO ligand and O—C 1.239 (4) Å for the pyCHO carbonyl group.     

Four (2,2′‐bipyridyl)(ferrocenyl)boronium derivatives

Crystal structures are reported for four (2,2′‐bipyridyl)(ferrocenyl)boronium derivatives, namely (2,2′‐bipyridyl)(ethenyl)(ferrocenyl)boronium hexafluoridophosphate, [Fe(C₅H₅)(C₁₇H₁₅BN₂)]PF₆, (Ib), (2,2′‐bipyridyl)(tert‐butylamino)(ferrocenyl)boronium bromide, [Fe(C₅H₅)(C₁₉H₂₂BN₃)]Br, (IIa), (2,2′‐bipyridyl)(ferrocenyl)(4‐methoxyphenylamino)boronium hexafluoridophosphate acetonitrile hemisolvate, [Fe(C₅H₅)(C₂₂H₂₀BN₃O)]PF₆·0.5CH₃CN, (IIIb), and 1,1′‐bis[(2,2′‐bipyridyl)(cyanomethyl)boronium]ferrocene bis(hexafluoridophosphate), [Fe(C₁₇H₁₄BN₃)₂](PF₆)₂, (IVb). The asymmetric unit of (IIIb) contains two independent cations with very similar conformations. The B atom has a distorted tetrahedral coordination in all four structures. The cyclopentadienyl rings of (Ib), (IIa) and (IIIb) are approximately eclipsed, while a bisecting conformation is found for (IVb). The N—H groups of (IIa) and (IIIb) are shielded by the ferrocenyl and tert‐butyl or phenyl groups and are therefore not involved in hydrogen bonding. The B—N(amine) bond lengths are shortened by delocalization of π‐electrons. In the cations with an amine substituent at boron, the B—N(bipyridyl) bonds are 0.035 (3) Å longer than in the cations with a methylene C atom bonded to boron. A similar lengthening of the B—N(bipyridyl) bonds is found in a survey of related cations with an oxy group attached to the B atom.     

Crystallographic report: A three‐dimensional coordination polymer: [Zn6(btc)4(4,4′‐bipy)5]n (btc = 1,2,4‐benzenetricarboxylate; 4,4′‐bipy = 4,4′‐bipyridine)

The three‐dimensional (3D) coordination polymer [Zn₆(btc)₄(4,4′‐bipy)₅]_n ( 1 ) (btc = 1,2,4‐benzenetricarboxylate; 4,4′‐bipy = 4,4′‐bipyridine) has been prepared hydrothermally. The zinc(II) centers in 1 are bridged by btc ligands to form a trinuclear subunit, which is further linked by 4,4′‐bipy and btc ligands to construct the 3D coordination architecture. Copyright © 2003 John Wiley & Sons, Ltd.     

Supramolecular interactions in a copper(II) 4′‐(4‐bromophenyl)‐2,2′:6′,2′′‐terpyridine complex

The title compound, [4′‐(4‐bromophenyl)‐2,2′:6′,2′′‐terpyridine]chlorido(trifluoromethanesulfonato)copper(II), [Cu(CF₃O₃S)Cl(C₂₁H₁₄BrN₃)], is a new copper complex containing a polypyridyl‐based ligand. The Cu^II centre is five‐coordinated in a square‐pyramidal manner by one substituted 2,2′:6′,2′′‐terpyridine ligand, one chloride ligand and a coordinated trifluoromethanesulfonate anion. The Cu—N bond lengths differ by 0.1 Å for the peripheral and central pyridine rings [2.032 (2) (mean) and 1.9345 (15) Å, respectively]. The presence of the trifluoromethanesulfonate anion coordinated to the metal centre allows Br...F halogen–halogen interactions, giving rise to the formation of a dimer about an inversion centre. This work also demonstrates that the rigidity of the ligand allows the formation of other types of nonclassical interactions (C—H...Cl and C—H...O), yielding a three‐dimensional network.     

Supramolecular Assemblies of (±-2,2''''-Dihydroxy-1,1''''-binaphthyl with 2,2''''-Bipyridine and Naphthodiazine

Introduction Optically active 1,1'-bi-2-naphthol (BINOL) and its derivatives have been widely used as chiral ligands of catalysts for asymmetric reactions and effective host compounds for the isolation or optical resolution of a wide range of organic guest molecules through the for-mation of crystalline inclusion complexes.1,2 The wide-ranging and important applications of these com-pounds in organic synthesis have stimulated great inter-est in developing efficient methods for their prepara-…     

Synthesis of 5‐[2‐(guanin‐9‐yl)‐ and 5‐[2‐(2‐aminopurin‐9‐yl)ethyl]‐2‐D‐ribo‐(1,2′,3′,4′‐tetrahydroxybutyl)‐1,3‐dioxane

Stereoselective synthesis of 5‐[2‐(guanin‐9‐yl)‐ and 5‐[2‐(2‐aminopurin‐9‐yl)ethyl]‐2‐D‐ribo‐(1′,2′,3′,4′‐tetrahydroxybutyl)‐1,3‐dioxane, 2‐5, as potential prodrugs of penciclovir, has been accomplished in six steps from readily available 2,3,4,5‐tetra‐O‐acetyl‐aldehydo‐D‐ribose ( 6 ) and the 1,3‐diol 7 . It has been demonstrated that the use of boron trifluoride diethyl etherate (BF₃·Et₂O) in dichloromethane along with excess anhydrous copper(II) sulfate was crucial for the efficient formation of cyclic acetal 8 . In addition, the chromatographic separation of cis and trans isomers of the cyclic acetal at the bromide stage 10 was feasible, which was requisite for the successful stereoselective synthesis of the ribosyl derivatives 2–5 .     

Poly[[trans‐diaquabis(μ2‐biphenyl‐2,2′‐dicarboxylato)bis(μ2‐4,4′‐bipyridine)dicobalt(II)] biphenyl‐2,2′‐dicarboxylic acid disolvate]

In the title compound, {[Co₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂(H₂O)₂]·2C₁₄H₁₀O₄}_n, each Co^II ion is six‐coordinate in a slightly distorted octahedral geometry. Both Co^II ions are located on twofold axes. One is surrounded by two O atoms from two biphenyl‐2,2′‐dicarboxylate (dpa) dianions, two N atoms from two 4,4′‐bipyridine (bpy) ligands and two water molecules, while the second is surrounded by four O atoms from two dpa dianions and two N atoms from two bpy ligands. The coordinated dpa dianion functions as a κ³‐bridge between the two Co^II ions. One carboxylate group of a dpa dianion bridges two adjacent Co^II ions, and one O atom of the other carboxylate group also chelates to a Co^II ion. The Co^II ions are bridged by dpa dianions and bpy ligands to form a chiral sheet. There are several strong intermolecular hydrogen bonds between the H₂dpa solvent molecule and the chiral sheet, which result in a sandwich structure.