Inorganic Chemistry Communications (v.61, #C)

Contents List (iii-xvii).

The in situ hydrothermal reaction of CuI, NaN3 and 4-(1H-imidazol-1-yl)benzonitrile leads to a new three-dimensional pillared-layer Cu(I)-MOF, [Cu2(μ 3-I)(μ 5 -IPT)]n (1) (HIPT = 5-[4-(imidazol-1-yl)phenyl]tetrazolate). Interestingly, the structure of 1 exhibits an unprecedented binodal (4, 8)-connected three-dimensional self-penetrating framework first constructed from [Cu4I2]2 + cationic clusters as 8-connected nodes and in situ generated IPT ligands as 4-connected nodes. Moreover, 1 is strongly luminescent with green emission (λ em  = 545 nm) in the solid-state.A new 3D pillared-layer metal–organic framework first formed from [Cu4I2]2 + cationic cluster and in situ generated tetrazole ligand has been synthesized and characterized, which exhibits an unprecedented (4, 8)-connected self-penetrating net with (43·63)2(46·618·84) topology. Moreover, Complex 1 is intense luminescent with green emission at room temperature.Display Omitted
Keywords: Cu-I cluster; In situ ligand synthesis; Crystal structure; Topology; Photoluminescence;

Ba(dl-C4H4O5) — An alkaline earth metal-dicarboxylate hybrid crystal with the synergy of multi-bonds by Chen Lei; Zheng Wang; Fangyuan Zhang; Zhihua Yang; Fangfang Zhang; Ying Wang; Shilie Pan (5-9).
The organic–inorganic hybrid crystal, Ba(dl-C4H4O5), has been firstly prepared by hydrothermal method. It crystallizes in monoclinic crystal system with a centrosymmetric space group of P21/c with a  = 8.150(2) Å, b  = 10.447(3) Å, c  = 6.938(2) Å, β  = 95.599(3)° and Z = 4. In this compound, the coexistence of organic ligand and the alkaline earth metal cation leads to the diversity of chemical bonds. The synergy of Ba–O ionic bonds and hydrogen bonds strengthens the crystal structure. Characterization of this earth metal-dicarboxylate hybrid crystal is described by using powder X-ray diffraction, infrared spectroscopy, UV–vis–NIR diffuse reflectance spectrum and the TG curve. In addition, Ba(dl-C4H4O5) possesses a short ultraviolet cutoff wavelength lower than 230 nm determined by the electronic transition of C–O group, which signifies the potential use in UV region applications. And the electronic structure and optical properties are studied by first principle calculation method, which obtains a birefringence value of 0.04.An alkaline earth metal-dicarboxylate hybrid crystal Ba(dl-C4H4O5) with high stable temperature has been prepared by hydrothermal method.Display Omitted
Keywords: Organic–inorganic hybrid; Metal-dicarboxylate; Crystal structure; DFT;

Three Ag(I)–cyanide coordination polymers with metal bonds tuned by N-heterocyclic ligands by Min Shao; Ming-Xing Li; Xue-Qin Wang; Heng-Hua Zhang (10-12).
Hydrothermal reactions of AgNO3, K3[Fe(CN)6] with N-heterocyclic ligands afforded three novel Ag(I)–cyanide coordination polymers, [Ag2(CN)2(tpt)] n (1), {[Ag(CN)(bpe)0.5][Ag(CN)]} n (2) and [Ag(CN)(btmb)0.5] n (3) (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine, bpe = 1,2-bis(4-pyridyl)ethane, btmb = 1,2-bis(1,2,4-triazol-1-ylmethyl)benzene). In complex 1, two Ag(CN) linear chains are bridged by bidentate tpt ligand to form a ladder-like structure, which are further connected by Ag―Ag metal bond to generate a 2D polymeric network. Complex 2 is an interesting 3D supramolecular architecture assembled by 2D [Ag1(CN)(bpe)0.5] n network and linear [Ag2(CN)] n chain combined by strong Ag―Ag metal bond. Complex 3 is a 1D ladder-like double-chain polymer constructed from Ag–cyanide linear chains and btmb spacer, which is further extended to a 2D supramolecular network by Ag–Ag weak interaction. The Ag–Ag metal interactions play important roles in the construction of three coordination polymers. Complexes 1 and 2 are respectively thermally stable at 300 and 180 °C. Complexes 1 and 3 emit strong blue luminescence.Three Ag(I)–cyanide coordination polymers were constructed based on different N-heterocyclic ligands. Complex 2 is an interesting 3D supramolecular architecture assembled by 2D [Ag1(CN)(bpe)0.5] n network and linear [Ag2(CN)] n chain combined by strong Ag―Ag metal bond. Complexes1 and 3 emit strong blue luminescence.Display Omitted
Keywords: Ag(I) complex; Cyanide; N-heterocycle; Crystal structure; Metal bond; Luminescence;

A 3D porous metal–organic framework {[Cu(4-tba)2](solvent)} n (1⋅S) is assembled via 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Htba) and Cu(II) nodes, which shows the [2 + 2] roto-translational interpenetrating network. Interestingly, 1 displays high CO2 adsorption selectivity over CH4/H2/O2/Ar/N2 gases, and acts an efficient catalyst precursor in some C–N/C–C bond formation reactions, including Chan–Lam coupling reaction of phenylboronic acid with imidazole, Suzuki–Miyoura coupling reaction of phenylboronic acids with aryl halides, and Heck coupling reaction of styrene with aryl halides.This work presents a novel 3D porous metal–organic framework, which can behave as a highly efficient catalyst for multiple C–N/C–N bond formation reactions.Display Omitted
Keywords: Cu(II) metal–organic framework; 4-(1H-1,2,4-triazol-1-yl)benzoic acid; C–N/C–C bond formation reactions; Catalysis;

Three unprecedented high-connected 3D lanthanide–organic frameworks based on benzene-1,2,4,5-tetracarboxylic acid by Jia-Jun Yang; Xiao-Yang Yu; Yu-Hui Luo; Hong Zhang; Wei-Ping Gao (16-20).
Three unprecedented high-connected 3D lanthanide coordination polymers based on benzene-1,2,4,5-tetracarboxylic acid (H4bta), {[Ln2(bta)1.5(H2O)4] · 3H2O}n (Ln = La (1) and Ce (2)) and [Pr(bta)0.5(H2bta)0.5(H2O)]n (3), have been synthesized under hydrothermal conditions. Complexes 1 and 2 show trinodal (4,4,10)-connected 3D network structures consisting of tetranuclear metal clusters bridged by bta4 − ligands, and a chair conformation hexamer water cluster can be found within the cage enclosed by eight neighboring tetranuclear metal clusters in the two complexes. While 3 consists of 2D {Pr(bta)0.5}n layers linked by H2bta2 − ligands, resulting in an unprecedented trinodal (4,6,10)-connected 3D topological network. The organic ligand exhibits five kinds of coordination modes, in which one of them is reported for the first time. Moreover, the luminescent properties of 13 have also been investigated.Two kinds of unprecedented high-connected 3D lanthanide–organic frameworks based on benzene-1,2,4,5-tetracarboxylic acid have been hydrothermally synthesized, and a chair conformation hexamer water cluster could be found within the cage enclosed by eight neighboring tetranuclear metal clusters in framework 1.Display Omitted
Keywords: Lanthanide coordination polymers; Benzene-1,2,4,5-tetracarboxylic acid; Topological structure; Water cluster; Luminescence;

Synthesis of acyclic diaminocarbene palladium complex featuring triethoxysilane moiety by Valentin A. Rassadin; Anton A. Yakimanskiy; Evgeniy V. Eliseenkov; Vadim P. Boyarskiy (21-23).
The first example of an acyclic diaminocarbene palladium complex, viz. cis-[PdCl2(CN(2,6-Me2C6H3)){C(NH(2,6-Me2C6H3)) = NH(CH2)3Si(OEt)3}], featuring the triethoxysilane moiety is described. The complex was generated from bis(o-xylylisocyanide)palladium dichloride and (3-aminopropyl)triethoxysilane under mild conditions and isolated in 88% yield. The target compound is stable at RT either in the solid state or in CDCl3 or CD3OD solutions within several months.Display Omitted
Keywords: Acyclic diaminocarbenes; Palladium complex; Isocyanides; Nucleophilic addition; Ligand reactions; (3-Aminopropyl)triethoxysilane;

An unprecedented 3D manganese(II) MOF displaying (4,5)-connected xah topology by Xiao-Xiao Wang; Ya-Mei Yu; Dian-Heng Huan; Kristof Van Hecke; Guang-Hua Cui (24-26).
An unusual 3D manganese(II) coordination polymer based on the flexible bis(benzimidazole) ligand, namely, [Mn(L)(ndc)] n (L = 1,4-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene, H2ndc = 2,6-naphthalenedicarboxylic acid), was synthesized and characterized by IR, elemental analysis, thermal gravimetric and single-crystal X-ray diffraction. The complex exhibits an unprecedented three-fold interpenetrating xah architecture with a (4,5)-connected (42.62.82)(46.64) topology, which represents the first binodal (4,5)-connected xah network observed in coordination polymers. The fluorescence and catalytic properties of the complex for the degradation of the Congo red dye in a photo-Fenton-like process were investigated.A 3D Mn(II) framework has been constructed with the flexible bis(benzimidazole) and 2,6-naphthalenedicarboxylic acid co-ligand, which features a unique (4,5)-binodal three-fold interpenetrating xah architecture. In addition, the compound exhibits catalytic activity for the degradation of the Congo red dye in a photo-Fenton-like process.Display Omitted
Keywords: Bis(benzimidazole); Catalytic property; Coordination polymer; Manganese(II);

Two new 3D metal–organic frameworks (MOFs), [NH2(CH3)2][KZn(DMTDC)2] (1) and [NH2(CH3)2][NaZn(DMTDC)2] (2), have been solvothermally synthesized and structurally characterized. Both 1 and 2 exhibit 3D structures with 1D infinite helical K–O–Zn and Na–O–Zn metallic chains. Meanwhile, stability studies indicate that 1 was robust even after immersed in various solvents and heated in the air. Furthermore, the N2 and CO2 adsorption isotherms of 1 and 2 were also measured.Two 3D frameworks with 1D infinite helical K–O–Zn (1) and Na–O–Zn (2) chains have been synthesized, and both of them exhibit high stabilities after exposed to water, different solvents and even heated in the air.Display Omitted
Keywords: Metal–organic framework; Stability; Adsorption properties;

A cyclometalated iridium(III) complex that induces apoptosis in cisplatin-resistant cancer cells by Jin-Quan Wang; Xiao-Juan Hou; Hua-Ben Bo; Qi-zhu Chen (31-34).
A novel cyclometalated iridium(III) complex, [Ir(CˆN)2(HPIP)]Cl (IrC) was synthesized and characterized. IrC exhibited about 10-fold higher cytotoxicity than cisplatin against A549 cancer cell line. Interestingly, a cisplatin-resistant cell line, A549-CP/R showed sensitivity to IrC. Further study suggested that IrC induced apoptosis via negatively regulated the nuclear factor-kappa B (NF-κB) pathway, which involved reactive oxygen species (ROS) generation, Bcl-2 and caspase family members activation. Taken together, these results suggest that IrC is able to overcome chemoresistance and may be an effective treatment for platinum-resistant cancer therapy.A novel cyclometalated iridium(III) complex avoids cisplatin resistance and induces apoptosis via the nuclear factor-κB/reactive oxygen species pathway in A549 cisplatin-resistant human lung cancer cells.Display Omitted
Keywords: Iridium(III) complex; Platinum resistance; ROS; NF-κB; Apoptosis;

In the present communication, we have reported the construction of a series of Cd(II)-MOFs using conformationally flexible ligand (CFL); 3,3′,5,5′-tetramethyl-4,4′-bipyrazolyl (H2BPz), flexible bent ligand (FBL); methylenebis-(3,5-dimethylpyrazole) (H2MBPz) and positional isomer of naphthalene disulfonic acid salt ligands (1,5-NDS, 2,6-NDS). By using these ligands, four new coordination polymers namely [Cd(H2MBPz)2∙ 1,5-NDSA]n (NDS-MOF-1), [Cd(H2BPz)∙ 1,5-NDSA]n (NDS-MOF-2), {[Cd(H2MBPz)2]2 +∙ 2,6-NDSA2 −}n (NDS-MOF-3) and {[Cd(H2BPz)2]2 +∙ 2,6-NDSA2 −}n (NDS-MOF-4) have been synthesized. The crystal structure analysis revealed that the employment of positional isomeric naphthalene disulfonic acid salts resulted in different architectures ranging from one dimensional chain to two dimensional grid network and further connected into a three dimensional supramolecular structure through intermolecular hydrogen bonds, π⋯π and C–H⋯π interactions. In addition, the photophysical properties and thermal stability studies for all the NDS-MOFs 1–4 were also investigated.The MOFs 1–4, [Cd(MBPz)2∙ 1,5-NDSA]n (NDS-MOF-1), [Cd(BPz)∙ 1,5-NDSA]n (NDS-MOF-2), {[Cd(MBPz)2]2 +∙ 2,6-NDSA2 −}n (NDS-MOF-3) and {[Cd(BPz)2]2 +∙ 2,6-NDSA2 −}n (NDS-MOF-4) were synthesized from cadmium nitrate and respective mixed ligands system i.e. 1,5-NDS and 2,6-NDS system by means of layering techniques. Furthermore, photophysical properties and thermal stability of frameworks were also investigated. Comparative study of Cis-Trans conformation of H2BPz and H2MBPz ligand by changing the position of sulfonate from α to β position of naphthalenedisulfonate was scrutinized.Display Omitted
Keywords: Cadmium(II); Coordination polymers; Conformation; Naphthalenedisulfonate; Thermal stability; Photophysical properties;

Structures and properties of new ferrocene-based paramagnetic anion octamethylferrocenedisulfonate and its TTF salt by Hiroki Akutsu; Ryuichiro Hashimoto; Jun-ichi Yamada; Shin'ichi Nakatsuji; Yasuhiro Nakazawa; Scott S. Turner (41-47).
The structure and properties of a new ferrocene-based disulfonate anion, octamethylferrocenedisulfonate (Fe(C5(CH3)4(SO3))2), obtained as tetraphenylphosphonium (PPh4) salts, are described. Recrystallisation gave two types of salts, yellow crystals and green powder. The former composition was found to be (PPh4)2[Fe(C5(CH3)4(SO3))2], where Fe(C5(CH3)4(SO3))2 is dianionic. The green powder was determined to be (PPh4)[Fe(C5(CH3)4(SO3))2]·0.4H2O, in which the iron complex is monoanionic despite it having two anionic sulfo groups. The ferrocenyl part has a charge of + 1 and temperature-dependent magnetic susceptibility indicates that the green salt is paramagnetic. Metathesis of either PPh4 salts with (TTF)3(BF4)2 (TTF = tetrathiafulvalene) gave the same compound, (TTF)[Fe(C5(CH3)4(SO3))2]·3.5H2O, in which the anion is paramagnetic. This is the first TTF-type salt that contains a non-diamagnetic ferrocenyl-based counter-ion. The structure and properties of the TTF salt are reported.New ferrocene-based paramagnetic anion octamethylferrocenedisulfonate and its TTF-based charge transfer salt were prepared.Display Omitted
Keywords: Ferrocene; Tetrathiafulvalene; Crystal structure; Charge-transfer salt; Organic conductors;

Study on a new cyclodextrin based metal–organic framework with chiral helices by Hongjun Lu; Xiaoning Yang; Shuxian Li; Yu Zhang; Jingquan Sha; Changde Li; Jingwen Sun (48-52).
Staring from β-cyclodextrins and Na salts, a new metal–organic framework with chiral helices, (C42O35H70)2(NaOH)4·H2O (CD-MOF-1), has been successfully synthesized. X-ray diffraction analysis reveals that CD-MOF-1 exhibits a 3D framework with left-handed helical channels running through the structure created by the ligation of Na ions to the primary and secondary faces of the β-cyclodextrins rings. Additionally, inclusion properties of CD-MOF-1 were also studied, and the result shows that the inclusion rate using CD-MOF-1 as inclusion materials is higher than that of β-cyclodextrins, which is expected to become a new type of green crystal material from edible natural products.The first example of MOF based on β-CD with the left-handed chiral helical was reported, which was constructed by the ligation of Na ions to the primary and secondary faces of the β-CD rings.Display Omitted
Keywords: Synthesis; Cyclodextrins; Metal–organic framework; Inclusion; 5-FU;

Despite tremendous efforts, designing and preparing water, chemical, and moisture stable porous coordination polymers (PCPs) with carboxylate ligands remain a challenge. Here, we firstly and systemically investigated the roles of rod-packed organic units for preparing the stable PCPs with different carboxylate ligands. The experimental results demonstrated that the rod packed organic units with short distance of adjacent ligands, bridged by La3 + metal chain, can form water, chemical, and moisture stable PCPs.We firstly and systemically investigate the stability of four La-based PCPs with carboxylate ligands, and demonstrate a new method via bridging of La3 + metal chain by rod packed organic units for accessing stable PCPs.Display Omitted
Keywords: Porous coordination polymers; Rod-packed organic units; Stability; La; Adsorption;

A novel 3D Zn(II) complex [Zn(H2hmIDC)]n (1) has been synthesized through the reaction of an achiral ligand 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid (H4hmIDC) with Zn(NO3)2. Single crystal X-ray diffraction determination shows that complex 1 is the first 3D framework based on left and right-handed helical chains, in which all of the H2hmIDC2 − ligands coordinate to Zn(II) ions with μ3-bridging mode. The overall structure of complex 1 can be described as a (3,3)-connected topology with the topological notation of {82·10}2. The TG analysis shows that it possesses great thermal stability. In addition, its IR spectra, PXRD pattern and fluorescence property have been investigated.A new 3D complex, [Zn(H2hmIDC)]n (1), which contains left- and right-handed helical chains has been synthesized and characterized by single crystal X-Ray diffraction. Additionally, its IR spectra, PXRD pattern, thermogravimetric and fluorescence property are also investigated.Display Omitted
Keywords: Zn(II) complex; Chiral chain; Thermostability; Fluorescence;

A novel coordination network of Tb(III) with 2-hydroxy-trimesic acid showing very intense photoluminescence by Xue Liu; Sebastiaan Akerboom; Sven H.C. Askes; Ilpo Mutikainen; Elisabeth Bouwman (60-63).
A novel coordination network consisting of Tb(III) ions and 2-hydroxy-trimesic acid (H4 L) has been prepared and characterized using infrared spectroscopy, elemental analysis, thermogravimetric analysis and single crystal X-ray crystallography. The structure forms a rigid three-dimensional network, which is described by the formula [Tb(HL)(H2O)2]n. The compound shows emission lines characteristic for Tb(III) when excited with near-UV radiation. The quantum yield of this process is 67%, showing that the ligand acts as a highly efficient antenna for sensitizing Tb(III) emission and that the complex TbHL potentially is a good phosphor for WLED.A novel coordination network consisting of Tb(III) ions and 2-hydroxytrimesic acid (H4L) reveals a rigid three-dimensional network described by the formula [Tb(HL)(H2O)2]n. Bright green luminescence with a quantum yield of 67% is observed when the compound is excited with near-UV radiation, showing that the ligand acts as a highly efficient antenna for sensitizing Tb(III) emission.Display Omitted
Keywords: Lanthanoids; Luminescence; Metal-organic framework; WLED;

Two novel 3D self-threading coordination polymers with CdSO4 topology: Syntheses, structures and properties by Yu-Ci Xu; Yu Chen; Xu Li; Qi Yang; Jin-Lin Zhang; Hui-Ling Xu; Xiao-Shan Zeng; Xi-Chi Wang; Dong-Rong Xiao (64-67).
Two new isostructural metal-organic frameworks, namely [Co(HL)(bpp)] · 0.5H2O (1) and [Zn(HL)(bpp)] · 3H2O (2) (H3L = 5-(2′-carboxy-biphenyl-4-ylmethoxy)-isophthalic acid, bpp = 1,3-bis(4-pyridyl)propane), have been hydrothermally synthesized and further characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, IR spectra and TG analyses. Compounds 1 and 2 exhibit interesting 3D frameworks of (65.8)-CdSO4 topology with dangling arm (i.e. the uncoordinated 2′-carboxy-biphenyl-4-ylmethoxy group of HL ligand). The remarkable feature of these two compounds is that each dangling arm threads into two 6-membered rings belonging to the 3D net itself, displaying the self-threading character. The magnetic properties of 1 and photoluminescence of 2 have also been investigated.Two novel 3D self-threading metal-organic frameworks with CdSO4 topology, which add new members to the newborn self-threading family, are reported.Display Omitted
Keywords: Entangled network; Self-threading; CdSO4 topology;

Two octamolybdate-based hybrids functionalized by 1,3-bis[tris(hydroxymethyl)methylamino]propane ligand by Hailou Li; Bo Shao; Yanyan Li; Lijuan Chen; Junwei Zhao (68-72).
Two octamolybdate-based organic–inorganic hybrids functionalized by 1,3-bis[tris(hydroxymethyl)methylamino]propane (H6bthmap) Na2H4[γ-Mo8O26(H5bthmap)2]·2H2O (1) and [NH4]6{[Cu(H3bthmap)]2(β-Mo8O26)} (2) have been synthesized through the aqueous synthetic method and structurally characterized by elemental analyses, IR spectra, UV spectra, thermogravimetric (TG) analysis and single-crystal X-ray diffraction. X-ray crystallography reveals that 1 consists of a classic [γ-Mo8O26]4 − polyoxoanion decorated by two flexible [H5bthmap] ligands through two O atoms from two [H5bthmap] ligands and 2 contains a [β-Mo8O26]4 − polyoxoanion with bisupporting [Cu(H3bthmap)] anions via two terminal O atoms from the [β-Mo8O26]4 − polyoxoanion. As far as we know, 1 and 2 represent the first octamolybdate-based hybrids with 1,3-bis[tris(hydroxymethyl)methylamino]propane ligands. The TG curves of 1 and 2 indicate two steps of weight loss and three steps of weight between 25 and 980 °C, respectively. Furthermore, the electrochemical and electrocatalytic properties of 1 and 2 have been investigated.Two octamolybdate-based hybrids functionalized by 1,3-bis[tris(hydroxymethyl)methylamino]propane (H6bthmap) Na2H4[γ-Mo8O26(H5bthmap)2]·2H2O and [NH4]6{[Cu(H3bthmap)]2(β-Mo8O26)} were synthesized and characterized.Display Omitted
Keywords: Polyoxometalate; Octamolybdate; 1,3-Bis[tris(hydroxymethyl)methylamino]propane; Electrocatalysis;

The thermal decomposition of manganese and cobalt-terephthalate Metal-Organic Framework precursors was utilized as a synthetic route for fabrication of Co3O4, Mn3O4 and Mn2O3 nanoparticles. The prepared metal oxide nanoparticles of Co3O4, Mn3O4 and Mn2O3 possess average size diameter of 40, 60 and 80 nm respectively. The findings demonstrate that spinel structure nanoparticles of Co3O4 and Mn3O4 exhibit efficient catalytic activity toward heterogeneous olefin epoxidation in the presence of tert-butyl hydroperoxide. In addition, Co3O4 and Mn3O4 nanoparticles illustrated excellent catalytic stability and reusability for nine and four cycles, respectively, toward olefin oxidation.Spinel structured Mn3O4 and Co3O4 and Mn2O3 nanoparticles were prepared by thermal decomposition of manganese and cobalt-terephthalate Metal-Organic Framework (MOF) precursor at 400, 500 and 600 °C. Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared and X-ray diffraction spectrometry were used to characterize the phase and the morphology of the metal oxide nanoparticles. Characterization of prepared nanoparticles was indicated that these nanoparticles have average size diameter 60, 40 and 80 nm for Mn3O4, Co3O4 and Mn2O3 respectively. Catalytic efficacy of Mn3O4 and Co3O4 nanoparticles was evaluated in the epoxidation of a variety of alkenes using tert-butyl hydroperoxide as an oxidant. In addition, metal oxide nanoparticles exhibited excellent catalytic stability in several runs, demonstrating that these heterogeneous and recyclable catalysts are promising for olefin epoxidation.Display Omitted
Keywords: Metal-oxide nanoparticles; Epoxidation reaction; Heterogeneous catalyst; Recyclable catalyst;

A new supramolecular adduct 4-trifluoromethoxyanilinium hexafluorophosphate-1,4,7,10,13,16-hexaoxacyclooctadecane ([C7H7NOF3–(18-crown-6)]+[PF6]) was synthesized and separated as crystals. DSC measurement detected that this compound undergoes a reversible phase transition at about 158 K with a heat hysteresis of 4.8 K. The single crystal X-ray diffraction data obtained at 213 K and 113 K suggest that the phase transition undergoes from a high temperature phase with a space group of Pnma to a low temperature one with a space group of P21/n, the symmetry breaking occurs with an Aizu notation of mmmF2/m. The driving force of the transition may be ascribed to the order–disorder transformation of the inorganic PF6 anion. Broad peak dielectric anomaly observed at 157 K further confirms this phase transition.One reversible phase transition supramolecular adduct is synthesized. DSC measurement detected the phase transition point of 158 K. The single crystal X-ray diffraction data obtained at 213 K and 113 K suggest that the phase transition undergoes from a high temperature phase with a space group of Pnma to a low temperature one with a space group of P21/n. Distinct dynamic behavior of the inorganic anion maybe the driving force for the phase transition.Display Omitted
Keywords: Structural phase transition; Dielectric anomaly; Symmetry breaking; Supramolecular host–guest compounds;

A combined experimental and theoretical investigation on solvent-dependent luminescence behavior of a Cu(I)-MOF by Jun Wang; Chu-Ying Gu; Qing-Lin Li; Lu Lu; Jian-Qiang Liu; Wei-Cong Liu; Reena Yadav; Abhinav Kumar; Seik Weng Ng (82-84).
A new Cu(I)-based complex with chemical formulae [Cu7(CN)7(4,4′-bipy)] (1), (4,4′-bipy = 4,4′-bipyridine) has been synthesized and structurally characterized. Single-crystal X-ray analyses reveal that compound 1 exhibits threading network constructed by a 2D sheet and 1D chain. The photoluminescent property of 1 in different solvents has been investigated and corroborated by theoretical calculations. The obtained results are in good agreement with the results of solvent-dependent luminescence experimental behaviors. An extended analysis of experimental and computational result for 1 indicates that strong metal–solvent bonding interaction plays a dominant role in the sensing of various solvents.A new Cu(I)-based complexes shows a threading network constructed by a 2D sheet and 1D chain. The order of calculated energy gaps is in good agreement with the result of solvent-dependent luminescence experimental behaviors.Display Omitted
Keywords: Threading network; Luminescence; Sensing effect;

A novel coordination polymer based on the multidentate N-donor ligand 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole (3,3′-tmbpt) and 1,2,4,5-benzenetetracarboxylate anion (btec), namely, [Zn5(3,3′-tmbpt)(btec)2(OH)2] (1), has been synthesized hydrothermally. Compound 1 displays a rare 3D (3,4,11)-connected framework based on a [Zn5(OH)2]8 + cluster. The optical band gap and photoluminescent property of compound 1 have been studied.A novel coordination polymer with (3,4,11)-connected structure has been prepared under hydrothermal condition, where its photoluminescent property and optical band gap have also been studied.Display Omitted
Keywords: Pentanuclear cluster; Highly connected; Coordination polymer; Optical band gap; Photoluminescence;

Two novel Pb(II) complexes, {[Pb1.5(BPTC)]∙0.25H2O}n(1) and {[Pb(ADC)·(H2O)]}n(2), (H3BPTC = biphenyl-3,2′5′-tricarboxylate, H2ADC = 1,3-Adamantanedicarboxylic acid) were successfully synthesized through varying the different polycarboxylate ligands. The compounds were structurally characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compound 1 exhibits a 3D porous coordination framework, which possesses a new 3-nodal (5,6,8)-connected topology. Compound 2 shows a two-dimensional layer containing a 1D nanotube structure. In addition, compounds 1 and 2 exhibit high thermal stability and fluorescent properties in the solid state at room temperature.Two novel Pb(II) complexes were successfully synthesized through varying the different polycarboxylate ligands. Compound 1 exhibits a 3D porous coordination framework, which possesses a new 3-nodal (5,6,8)-connected topology. Compound 2 shows a two-dimensional layer containing a 1D nanotube structure. In addition, compounds 1 and 2 exhibit high thermal stabilities and fluorescent properties at room temperature.Display Omitted
Keywords: PbII-coordination framework; Organic-acid ligands; Network topology; Fluorescence;

Tris(1-(chloromethyl)-1,4-diazabicyclo[2.2.2]octane) tetra(tetrafluoroborate) dichloride, [C7H15ClN2 2 +]3·[BF4 ]4·2Cl, was synthesized and separated as colorless rodlike crystals. Differential scanning calorimetry detected that this compound underwent a reversible phase transition at ca. 242.9 K with a hysteresis of 3.7 K width. Single crystal X-ray diffraction data suggested that a room-temperature phase with a space group of Pnma (a = 20.0644(12) Å, b = 7.3121(4) Å, c = 25.6369(15) Å, V = 3761.3(4) Å3 and Z = 4) was transited to a low temperature one with a space group of P21/c (a = 7.184(3) Å, b = 25.579(10) Å, c = 20.074(8) Å, β = 91.348(6)°, V = 3688(3) Å3 and Z = 4), and symmetry breaking occurred with an Aizu notation of mmmF2/m. The order–disorder transition of BF4 anions and the ordering of twisting motions of dabco rings may drive the phase transition.A novel mononuclear metal–organic compound, tris(1-(chloromethyl)-1,4-diazabicyclo[2.2.2]octane) tetra(tetrafluoroborate) dichloride, [C7H15ClN2 2 +]3·[BF4 ]4·2Cl, was synthesized. X-ray diffraction data suggested that the phase transition undergoes from a room temperature phase with a space group of Pnma to a low temperature one with a space group of P21/c, and symmetry breaking occurred with an Aizu notation of mmmF2/m.Display Omitted
Keywords: Differential scanning calorimetry; Phase transition; Symmetry breaking; Variable-temperature X-ray;

2-tetrahydrofurfurylamino-N,N-bis(2-methylene-4-tert-butyl-6-methyl)phenol reacts with CoCl2·6H2O to provide one cobalt(II) complex [LCoNCMe] 1, whose structure has been determined by X-ray diffraction. 1 can electrocatalyze hydrogen evolution from water with a turnover frequency (TOF) of 160.78 mol of hydrogen per mole of catalyst per hour at an overpotential of 889 mV (pH 7.0).A new molecular catalyst based on cobalt complex [LCoNCMe] 1 with an amine-bis(phenolate) ligand can electrocatalyze hydrogen evolution from water with a turnover frequency (TOF) of 160.78 mol of hydrogen per mole of catalyst per hour at an overpotential of 889 mV (pH 7.0).Display Omitted
Keywords: Cobalt(II) complex; X-ray structure; Molecular electrocatalyst; Water reduction; Hydrogen evolution;

Opening catalytically active sites in metal organic frameworks is an issue of fundamental importance for the development of effective and efficient catalysts. In this work, we first reported two metal metalloporphyrin–organic frameworks (MMPFs) with unoccupied pyridine groups as base catalysts. The reaction of Mn(II) and Co(II) with 5,10,15,20-tetrapyridylporphyrin produces two different metal metalloporphyrin–organic frameworks, {[(MnTPyP)]·H2O}n (MMPF-Mn) and [(CoTPyP)]n (MMPF-Co) (TPyP = 5,10,15,20-tetrapyridylporphyrin) under hydrothermal conditions. These two MMPFs have been fully characterized by single-crystal X-ray diffraction, powder XRD, elemental analysis and thermogravimetry (TG). MMPF-Mn displays a 3D network with a nbo topology, large and open hexagonal channels, MMPF-Co reveals a 1D single zigzag chain architecture. Interestingly, both MMPFs have a high thermal stability and opening basic pyridine group, which have been tested for the base catalyzed Knoevenagel condensation reaction. The catalytic study has demonstrated that MMPF-Mn catalysts having exposed pyridine group within 1D channel displayed an excellent performance for Knoevenagel condensation reaction. When MMPF-Mn was recycled four times, its catalytic activity remained with an inconspicuous decrease. We attribute MMPF-Mn showing a better performance than MMPF-Co to its active sites being aligned in extra-large cavity with an interior diameter of 20 Å.In this work, we first reported two metal metalloporphyrin–organic frameworks (MMPFs) with unoccupied pyridine groups as base catalysts. The reaction of Mn(II) and Co(II) with 5,10,15,20-tetrapyridylporphyrin produces two different metal metalloporphyrin–organic framework, {[(MnTPyP)]·H2O}n (MMPF-Mn) and [(CoTPyP)]n (MMPF-Co) (TPyP = 5,10,15,20-tetrapyridylporphyrin) under hydrothermal conditions. MMPF-Mn displays a 3D network with a nbo topology, large and open hexagonal channels, MMPF-Co reveals a 1D single zigzag chain architecture. Interestingly, both MMPFs have a high thermal stability and opening basic pyridine group, which have been tested for the base catalyzed Knoevenagel condensation reaction. The catalytic study has demonstrated that MMPF-Mn catalysts having exposed pyridine group within 1D channel displayed an excellent performance for Knoevenagel condensation reaction. When MMPF-Mn was recycled four times, its catalytic activity remained with an inconspicuous decrease. We attribute MMPF-Mn showing a better performance than MMPF-Co to its active sites being aligned in extra-large cavity with an interior diameter of 20 Å.Display Omitted
Keywords: Porphyrin; Base catalysis; Solid catalyst; Knoevenagel condensation reaction;

Two novel coordination polymers, [Co(1,4-ndc)(bipe)] (1), [Cd2(bdc)2(bipe)2]·2H2O (2) (bipe = bis(4-imidazolphenoxy)ethane, H2bdc = 1,4-benzenedicarboxylic acid and 1,4-H2ndc = naphthalene-1,4-dicarboxylic acid), have been synthesized and structurally characterized. Compound 1 features a five-fold interpenetration of dia network in a [3 + 2] mode. Compound 2 shows an eight-fold interpenetration of dia network in a [4 + 4] mode. In addition, compound 2 shows an emission at 435 nm when it was excitated at 332 nm.Display Omitted
Keywords: Coordination polymers; Entanglement; Diamondoid network; [3 + 2] mode; [4 + 4] mode;

A novel organic–inorganic hybrid supramolecular compound, [(4-Nitroanilinium)(18-crown-6)][BF4](CH3CN), was prepared via H-bond dipole interactions between 4-nitroanilinium, 18-crown-6, and BF4 , in acetonitrile solution. N–H…O hydrogen bonds between neighboring 4-nitroanilinium cations and 18-crown-6 were observed. However, the formation of one-dimensional supramolecular chain structure via N–H…O that contacts through the cavity of 18-crown-6 was worth noting. A strong dielectric response was observed above 300 K at a low frequency of 500 Hz, thereby suggesting the proton transfer in the N–H…O bonds.a) View of the self-assembly packing of 18-crown-6 and 4-nitroanilinium along the b-axis in complex 1, showing N–H…O hydrogen bond interactions in the one-dimensional chain structure through the cavity of 18-crown-6. Blue ring represents 18-crown-6. b) Dielectric constants of complex 1 measured along the b-axis at frequencies of 500 Hz to 1 MHz.Display Omitted
Keywords: Crystal structure; One-dimensional arrangement; Dielectric properties; Proton transfer; N–H…O hydrogen bond; 4-nitroanilinium; 18-crown-6;

A {PMo12O40}-directed organic–inorganic hybrid compound H3O[Mo6(bpy)6O17][PMo12O40]·2H2O (1) (bpy = 2,2′-bipyridine) has been hydrothermally synthesized and characterized by the elemental analysis, IR, XRD, TG analysis and single-crystal X-ray diffraction. In compound 1, Keggin heteropolyanions as templates induce the [MoO4(bpy)] complexes to form unusual wave-liked hexa-molybdenum unit's chains, which are further linked to form pure Mo-oxide-based host layers via supramolecular interaction. {PMo12} as guest units is grafted on the host layer to result in Keggin ions layers. The host cation layers and Keggin ions layers alternately array together to form unique sandwich-type supramolecular networks. In addition, the solid state fluorescent properties, and electro- and photo-catalytic behaviors of compound 1 have been studied.Keggin-type [PMo12O40]3 − anions as templates lead to an unusual hybrid materials, which present the first pure Mo-oxide-based coordination polymers based on hexa-molybdenum unit's chains and {PMo12} cluster. The solid state fluorescent properties, electro- and photo-catalytic behaviors of the compound have been studied.Display Omitted
Keywords: Supramolecular; [PMo12O40]3 −;  Coordination polymers; Photocatalytic activity; Electro-catalytic property;

The synthesis, structure and properties of a new compound with 1D linear chain arsenomolybdate anion building block by Wenqi Zhao; Zhanhua Su; Zhifeng Zhao; Bowen Cong; Lin Xia; Baibin Zhou (118-122).
The new inorganic–organic hybrid arsenomolybdate {Cu(2,2′-bpy)}2{H2As2Mo2O14} (2,2′-bpy = 2,2′-bipyridine) (1) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analyses, X-ray powder diffraction (XRPD), IR spectroscopy, UV spectroscopy, XPS spectroscopy and thermogravimetric analysis (TG). Compound 1 presents an infinite 1D chain structure based on the unprecedented {H2As2Mo2O14}4 − fragment and transition-metal complex {Cu(2,2′-bpy)}2 +. Compound 1 displays obvious electrocatalytic activities toward the reduction of nitrite and better photocatalytic activities for the degradation of methylene blue.Compound 1 presents an infinite 1D chain structure based on the unprecedented {H2As2Mo2O14}4 − fragment and transition-metal complex {Cu(2,2′-bpy)}2 +, which possesses obvious electrocatalytic activities toward the reduction of nitrite and better photocatalytic activities for the degradation of methylene blue.Display Omitted
Keywords: Arsenomolybdate; Electrocatalytic; Photocatalytic;

Two new coordination polymers, [Co3(μ 7-CTA)(bipy)(μ 3-OH)2(μ 2-H2O)]·3H2O (1) and [Mn2(μ 6-CTA)(bipy)(H2O)2]·H2O (2), have been prepared by a flexible cyclohexane-1,2,4,5-tetracarboxylic acid (H4CTA) with a chelating co-ligand, 2,2’-bipyridine (bipy). Complex 1 is a two-dimensional (2D) structure based on unusual hexanuclear cluster (Co6) nodes and CTA linkers, while 2 exhibits a 1D chain based on dinuclear cluster (Mn2) units and CTA linkers. Structural analysis revealed that the conformation of H4CTA in 1 exhibits a (a,e,e,a) fashion and transforms to a thermodynamically more stable conformation (e,a,e,e) type in 2. 1 and 2 showed antiferromagnetic interactions.Two cluster-based low dimensional coordination polymers constructed from conformation-flexible cyclohexanetetracarboxylate and chelating bipyridyl ligand, displaying various conformations and antiferromagnetic properties.Display Omitted
Keywords: Flexible conformation; Cyclohexane-1,2,4,5-tetracarboxylic acid; Coordination polymers; Crystal structure; Magnetic property;

Metal–organic framework MIL-53(Al)-supported copper catalyst for CO catalytic oxidation reaction by Zhi-Dou Tan; Hai-Yan Tan; Xin-Yu Shi; Zhuan-Ji; Yun-Fan Yan; Yin-Zhou (128-131).
Metal–organic framework (MOF) material MIL-53(Al) (MIL: Materials of Institut Lavoisier) with high thermal stability has been prepared by solvothermal method, serving as a support material of copper catalyst for CO oxidation. A comparison between the catalytic performance of the MIL-53(Al) and the Al2O3 support material was carried out to understand the catalytic behavior of the catalysts. The catalysts were characterized by thermogravimetric-differential scanning calorimeter (TG-DSC), N2 adsorption–desorption, X-ray diffraction (XRD), and transmission electron microscopy (TEM). The TG and N2 adsorption–desorption analyses showed that MIL-53(Al) had excellent stability and high surface areas. The highly dispersed CuO nanoparticles, which resulted from the three dimension porous structure of MIL-53(Al), give rise to a superior catalytic activity for CO oxidation. Indeed, the heterogeneous catalytic composite materials Cu/MIL-53(Al) catalyst exhibited much higher activity than the Cu/Al2O3 catalyst in CO oxidation test, with 100% conversion at 220 °C. The catalytic activity and structure of Cu/MIL-53(Al) catalyst were stable during the reaction.The highly dispersed CuO nanoparticles, which resulted from the three dimension porous structure of MIL-53(Al), give rise to a superior catalytic activity for CO oxidation.Display Omitted
Keywords: Metal–organic framework; Solvothermal synthesis; MIL-53(Al); Copper catalyst; CO catalytic oxidation;

Slow magnetic relaxation in a carboxylate-bridged one dimensional dysprosium complex by Shixiong She; Bingcheng Liu; Yan Yang; Zhaojing Ba; Li Gong; Bo Wang; Shixiong Min (132-135).
A new carboxylate-bridged dysprosium complex, e.g. [Dy2(PAA)6]n (1, PAA= 4-aminobenzoic acid anion), was synthesized under solvothermal conditions and fully characterized. Single crystal X-ray crystallography analysis reveals that complex 1 consists of linear chains built up by Dy2(PAA)6 units and bridged only by carboxylate groups. The magnetic studies indicate that the coordination polymer exhibits slow magnetic relaxation, suggesting single molecule magnet behavior.A new carboxylate-bridged one dimensional dysprosium complex, e.g. [Dy2(PAA)6]n (PAA  = 4-aminobenzoic acid anion) was obtained. The complex exhibits slow relaxation of magnetization.Display Omitted
Keywords: Dysprosium; Carboxylate-bridged; 1D chain; Single molecule magnet;

Two 3D coordination polymers constructed from flexible desymmetric carboxylate and neutral nitrogen ligands by Yun-Jie Ping; Ru-Yong Yan; Gao-Chao Zhao; Ling Qin; He-Gen Zheng (136-139).
Two coordination polymers based on a flexible desymmetric ligand precursor H2L have been synthesized, that is, [Ni(L)(dpe)3/2]• H2O (1), [Ni2(H2O)(L)2(bpp)2]• H2O (2), [H2L = 4,4′-(phenylazanediyl)dibenzoic acid, dpe = 1,2-di(pyridin-4-yl)ethane, bpp = 1,3-di(pyridin-4-yl)propane]. These complexes were characterized by elemental analysis, IR spectroscopy, X-ray single-crystal and power diffraction. In addition, the second nonlinear optical properties of 2 were measured.The solvothermal reactions afford two coordination polymers from a novel desymmetrized ligand, which was derived from the reported N,N,N′,N′-benzidinetetrabenzoic acid.Display Omitted
Keywords: Desymmetric ligand; Second harmonic generation; Coordination polymer;

X-ray crystallography reveals four isostructural lanthanide polymeric solids, [Ln2(atp)3(H2O)2]·dmf·4H2O (atp = 2-aminoterephthalate; dmf = N,N′-dimethylformamide; Ln = La (1), Ce (2), Pr (3) and Nd (4), respectively) that are obtained from the solvothermal synthesis which are crystallized in an interesting 3D polymeric framework with a (4,4,6)-linked {42·84}{44·62}2{48·66·8}2 fsy net topology. Upon excitation at 350 nm, they all show the solid state ligand-centered luminescences but both 2 and 3 also exhibit the weak lanthanide-based characteristic emissions in the visible region at room temperature. The cyclic voltammetric investigation indicates that 2 exhibits appreciable electrochemical activity for formaldehyde.Four isostructural lanthanide polymeric solids, [Ln2(atp)3(H2O)2]·dmf·4H2O (atp = 2-aminoterephthalate; dmf = N,N′-dimethylformamide; Ln = La (1), Ce (2), Pr (3) and Nd (4), respectively) were obtained under hydrothermal conditions, and crystallized in an interesting 3D polymeric framework with a (4,4,6)-linked {42·84}{44·62}2{48·66·8}2 fsy net topology. Their solid state luminescences in the visible region as well as the electrochemical behaviors for 2 have been investigated.Display Omitted
Keywords: Polymeric frameworks; Lanthanides; 2-Aminoterephthalate; Luminescence; Electrochemical properties;

Dinuclear group 4 alkoxides: Excellent initiators for ring-opening polymerization of cyclic esters by Jia-Xuan He; Yu-Lai Duan; Xin Kou; Yi-Zhou Zhang; Wei Wang; Ying Yang; Yong Huang (144-148).
Three new dinuclear group 4 metal alkoxides [Ti2(μ-O i Pr)(O i Pr)4L] (1), [Zr2(μ-O i Pr)(O i Pr)4L] (2) and [Hf2(μ-O i Pr)(O i Pr)4L] (3) have been prepared in good yields from the reaction of N, N-di(salicylidene)-2-hydroxyphenylmethanediamine (L-H3) and two equiv. [M(O i Pr)4(HO i Pr)n], respectively. Complexes 13 have been characterized by 1H NMR, 13C NMR, elemental analyses and X-ray diffraction analyses. The molecular structures of complexes 1 and 3 reveal dinuclear species in which the metal centers are hexa-coordinated to one oxygen atom and one nitrogen atom of the ligand, to two oxygen atoms of two isopropoxy groups, and to two bridging oxygen atoms of one phenolate group of ligand and one isopropoxy group. Complexes 13 are excellent catalysts/initiators for ring-opening polymerization of ε-caprolactone and L- and rac-lactide to give the corresponding polyesters.Three new dinuclear group 4 metal alkoxides [Ti2(μ-O i Pr)(O i Pr)4L] (1), [Zr2(μ-O i Pr)(O i Pr)4L] (2) and [Hf2(μ-O i Pr)(O i Pr)4L] (3) were successfully obtained. Complexes 13 are excellent catalysts/initiators for ring-opening polymerization of ε-caprolactone and L- and rac-lactide to give the corresponding polyesters.Display Omitted
Keywords: Group 4 complex;; Cyclic ester; Ring-opening polymerization; Initiator;

Morphology controlled nano-structures of a porphyrin dendrimer complex: Solvent effect on the self-assembly behavior by Feifei Song; Jingna Jia; Jimei Yu; Changlong Chen; Jijun Feng; Peihua Zhu (149-151).
The self-assembly properties of the porphyrin dendrimer complex in polar and non-polar solvents (methanol and n-hexane) have been comparatively studied. The present result appears to represent the first effort toward realization of controlling and tuning the morphology of self-assembled aggregates of porphyrin complexes through the solvent effect.A new porphyrin dendrimer complex (G2ZnPor) was designed and synthesized. Its self-assembly behavior and the semiconducting properties in polar and non-polar solvents (methanol and n-hexane) have been comparatively studied, indicating the effective influence of solvent on the morphology, dimension and the semiconducting properties of the assembled aggregates.Display Omitted
Keywords: Porphyrin; Dendrimer; Solvent effect; Self-assembly; Aggregates; Semiconductor;

Iridium(III) complexes based on 5-nitro-2-(2′,4′-difluorophenyl)pyridyl: Syntheses, structures and photoluminescence properties by Zhu-Qing Chen; Xuan Shen; Jia-Xin Xu; Hao Zou; Xin Wang; Yan Xu; Dun-Ru Zhu (152-156).
A series of cyclometalated Ir(III) complexes [Ir(dFNppy)2(PPh3)L] (PPh3  = triphenylphosphine, L = Cl, 1; NCS, 2; NCO, 3; N3 , 4) in which 5-nitro-2-(2′,4′-difluorophenyl)pyridyl (dFNppy) is used as the main ligand are synthesized and characterized. The crystal structures of 3 and 4 are determined by X-ray diffraction analyses. Photoluminescence spectra of 14 in CH2Cl2 solutions at room temperature show the maximum emission wavelengths (λ max) in the range from 586 to 627 nm, corresponding to red-orange luminescence. HOMO–LUMO energy levels of 14 are estimated by cyclic voltammetry measurements. Compared with corresponding 2-phenylpyridyl (ppy)-containing Ir(III) complexes having same ancillary ligands, 14 have obviously smaller HOMO–LUMO energy gaps (E g). Simultaneously, 14 show relatively bigger E g compared with 2-phenyl-5-nitropyridyl (5-NO 2 -ppy)-containing Ir(III) complexes possessing same ancillary ligands. Methods of E g adjustment are also discussed.Cyclometalated Ir(III) complexes containing 5-nitro-2-(2′,4′-difluorophenyl)pyridyl (dFNppy) are presented. Compared with corresponding ppy-containing Ir(III) complexes with same ancillary ligands, these complexes have obviously smaller E g. Simultaneously, these complexes show relatively bigger E g compared with 5-NO 2 -ppy-containing Ir(III) complexes with same ancillary ligands. The influence of nitro group on E g is much greater than that of fluorine atoms in these complexes.Display Omitted
Keywords: 5-Nitro-2-(2′,4′-difluorophenyl)pyridyl; Iridium(III) complex; Red-orange luminescence; HOMO–LUMO energy gap; E g adjustment;

Synthesis, structure and photocatalytic hydrogen evolution of a silver-linked hexaniobate Lindqvist chain by Haiying Wang; Zhijie Liang; Qisen Liu; Dongdi Zhang; Jingping Wang (157-159).
By using a combination of hydrothermal and diffusional strategies, a one-dimensional polyoxoniobate K5[H2AgNb6O19]·11H2O (1) has been synthesized. The structure was characterized by single-crystal X-ray diffraction, UV spectroscopy, TG analysis, PXRD and IR spectrum. 1 crystallizes in the hexagonal P63/mmc space group with a  = 9.8171(2) Å, c  = 16.5442(6) Å, and V  = 1380.84(6) Å3. It is the first Ag-containing polyoxoniobate, which consists of [H2AgNb6O19]5 − polyoxoanion and potassium ions. In addition, 1 exhibits the photocatalytic H2 evolution activity.The first Ag-containing PONb, K5[H2AgNb6O19]·11H2O, has been synthesized by “two-pot” methods and the photocatalytic activity of 1 has also been investigated.Display Omitted
Keywords: Polyoxoniobate; Lindqvist; Transition metals; Photocatalysis;

Three distinct 3D Co(II) coordination polymers have been prepared based on Co(OAc)2 and 5-methylnicotinate ligand (L-CH3) via different synthetic approaches, including layer diffusion, solvothermal synthesis, and ambient stirring method. Through the layer diffusion method, a 3D framework {[Co(L-CH3)2(H2O)0.5](CH3OH)1.25} n (1) can be obtained, which displays a 4-connect (66) dia topological network. Employment of solvothermal synthesis affords another 3D framework {[Co2(L-CH3)4(H2O)](H2O)} n (2), which shows a 5-connected (44  · 66) noz topology. {[Co(L-CH3)2(H2O)2](H2O)} n (3) can be produced from the ambient stirring method, featuring the 4-connected (42  · 64) lvt topology. These results demonstrate that fine-tunning on the diverse coordination motifs of 13 can be readily achieved by selecting proper synthetic approaches. In addition, thermal stability property of these complexes is also studied.Three distinct 3D CoII coordination polymers with 5-methylnicotinate ligand have been isolated through three different synthetic approaches, including layer diffusion, solvothermal, and stirring methods, which show the interesting dia, noz, and lvt topological nets, respectively.Display Omitted
Keywords: Coordination polymer; Synthetic approach; 5-Methylnicotinic acid; Structural diversity; Network topology;

Polymorphism is an important phenomenon to investigate the relationship between the chemical structures and properties of functional materials. Here, we demonstrate the existence of conformational polymorphism in the terahertz (THz) compounds of 2-[(E)-2-(4-hydroxy-3-methoxystyrl)-1-methyl]-quinolinium 4-chlorobenzenesulfonate (abbreviated as HMQ-CBS). There are two different crystalline phases (I and II, respectively). X-ray structural analyses reveal that HMQ-CBS crystallizes in the monoclinic crystallographic system with the non-centrosymmetric space group P c for phase-I, and centrosymmetric space group of P21/n for phase-II. These two different crystalline phases exhibit the distinct anionic orientations and crystal packings, leading to significantly different nonlinear optical (NLO) properties. Second harmonic generation (SHG) measurements reveal that crystals in phase-I possess the SHG efficiency of about 0.5 times that of N, N-dimethylamino-N-methylstilbazolium p-toluenesulphonate (DAST), which indicates that HMQ-CBS in phase-I might be a potential NLO crystal for THz application. In contrast, crystals in the phase-II show no SHG responses. Comparison of their crystal structures and NLO properties enables us to understand the correlation between molecular conformational changes and bulk NLO properties, and sheds light on the design of organic THz materials.The existence of conformational polymorphism in the terahertz (THz) compounds of 2-[(E)-2-(4-hydroxy-3-methoxystyrl)-1-methyl]-quinolinium 4-chlorobenzenesulfonate (HMQ-CBS) was identified. X-ray structural analyses reveal that HMQ-CBS crystallizes in the monoclinic crystallographic system with the non-centrosymmetric space group P c for phase-I, and centrosymmetric space group of P21/n for phase-II.Display Omitted
Keywords: Polymorphism; Nonlinear optics; THz crystal; Molecular packing;

A tetranuclear holmium compound exhibiting single molecule magnet behavior by Wei-Wei Kuang; Li-Li Zhu; Yun Xu; Pei-Pei Yang (169-172).
The synthesis, structure, and magnetic properties of a new tetranuclear holmium cluster [HoIII 4(μ 3-OH)2(L)4(piv)2(DMF)2]·2DMF (1) is reported, where the Schiff base H2L ligand is 2-hydroxy-3-methoxy-phenylsalicylaldimine and piv is pivalate. The cluster has a planar “butterfly” Ho4 core, which is bridged by two μ 3-hydroxide and six phenoxide oxygen atoms. Magnetically, compound 1 displays field-induced slow relaxation of magnetization. Fitting the dynamic magnetic data to the Arrhenius law gives energy barrier ΔE/kB  = 21.49 K and τ 0  = 6.97 × 10− 7  s.A new tetranuclear holmium compound, containing planar “butterfly” Ho4 core, has been obtained. Magnetically, the Ho4 cluster displays field-induced slow relaxation of magnetization with energy barrier ΔE/kB  = 21.49 K and τ 0  = 6.97 × 10− 7  s.Display Omitted
Keywords: Tetranuclear holmium cluster; Schiff base; Magnetic properties; Single molecular magnet;

A new lanthanide–organic framework formulated as TbL 1 (H3 L  = 9-(4-carboxy-phenyl)-9H-carbazole-3,6-dicarboxylic acid), was synthesized under hydrothermal reaction condition. Single-crystal X-ray diffraction analysis shows that 1 crystallizes in a hexagonal P65 space group with three-dimensional network and microporous structure. The desolventized framework of 1 shows much higher uptake of CO2 (43.7 cm3  g− 1) than that of CH4 (15.1 cm3  g− 1) at 1 atm and 273 K, which makes it a potential candidate for CO2/CH4 separation.A novel microporous Tb-based lanthanide–organic framework with a 6-connected topological structure exhibits high thermostability and selective adsorption capability for CO2 from CH4.Display Omitted
Keywords: Lanthanide–organic framework; Thermal stability; CO2 adsorption; Gas separation;

A lanthanide coordination polymer based on H2sfdb ligand, namely [Tb4(sdbc)4(phen)23-OH)4] n  ∙ 1.5nH2O (1) (H2sfdb = 4,4′-sulfonyldibenzoic acid, phen = 1,10-phenanthroline) has been hydrothermal synthesized and characterized. Compound 1 exhibits an unprecedented three-dimensional framework that comprised new cubane-like hydroxo clusters [Tb43-OH)4]8 + as the nodes and flexible (sfdb)2 − ligands as the linkers. In 1, (sfdb)2 − ligands display completely different four kinds of coordination modes. Interestingly, not only the carboxylate groups but also one oxygen atom of sulfonyl group of (sfdb)2 − ligand are coordinated with TbIII ions in 1, which is first found in the compounds based on H2sfdb ligand. The luminescence experiments show that TbIII compound exhibits the typical TbIII-centered luminescence.Four terbium(III) ions are bridged by four µ3-OH- groups to form a [Tb4(µ3-OH)4]8+ tetranuclear cluster, which is connected to the other eight terbium clusters though (sfdb)2- ligands to generate a novel 3D framework.Display Omitted
Keywords: Lanthanide; V-shaped dicarboxylate; Coordination polymer; Cubane-like hydroxo cluster; Luminescence;

NO3 -induced Salen-based Zn2Yb2 complex with good NIR luminescent property by Yan-E Luo; Yan Ma; Pei-Yang Su; Xing-Qiang Lü; Xun-Jin Zhu; Wai-Kwok Wong; Richard A. Jones (181-183).
Through the self-assembly of the Salen-type Schiff-base compound H 2 L (H 2 L  = N,N′-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine) with dehydrated Zn(NO3)2 and Ln(NO3)3 (Ln = La, Yb or Gd), the combination of novel μ 3-mode bridging, μ 2-chelating and free mode of six NO3 anions induces the formation of three complexes {[Zn2(L)2Ln2((μ 3-NO3)2(μ 2-NO3)2]⋅ 2(NO3)} (Ln = La, 1; Ln = Yb, 2 or Ln = Gd, 3), respectively, where the compacted Zn2Yb2-array of complex 2 endows the good NIR luminescence (Φ L Yb  = 0.98% and η sens  = 77%).In NO3  templated complex {[Zn2(L)2Yb2((μ 3-NO3)2(μ 2-NO3)2]⋅ 2(NO3)} (2), the combination of novel μ 3-mode bridging, μ 2-chelating and free mode of six NO3 anions causes the compacted Zn2Yb2-array with good NIR luminescence (Φ L Yb  = 0.98% and η sens  = 77%).Display Omitted
Keywords: Anion-templated Zn2Ln2-array; Multiple modes for NO3 anion; NIR luminescence;

A series of new complexes based on Keggin-type polyoxoanions (HTEA)2{[Na(TEA)2]H[SiW12O40]}∙5H2O (1), (HTEA)2{[Na(TEA)2][PW12O40]}∙4H2O (2) and (HTEA)2{[Na(TEA)2]H[GeW12O40]}∙4H2O (3) (TEA = triethanolamine) have been designed and synthesized. Single-crystal X-ray diffraction analyses reveal that compounds 1, 2 and 3 are isostructural, which exhibit the 1D chain structures consisting of Keggin-type polyoxoanions and {Na(TEA)2} linkers. Their structures were further characterized by XRD, IR spectroscopy, UV spectroscopy, elemental analyses, and thermogravimetric analysis. Moreover, compounds 13 present good the photocatalytic hydrogen evolution activities, which may be ascribed to the introduction of the sacrificial electron donors TEA to their structures, further, their photocatalytic hydrogen evolution activities are compared with its homologous Keggin-type heteropolyacid to verify the effect of TEA.The conventional photocatalytic system for hydrogen evolution requires both catalyst and sacrificial electron donor. Here, we firstly introduce the sacrificial electron donors into the structures of the POM anions and synthesize 3 new complexes. Their photocatalytic hydrogen evolution activities were compared with its homologous Keggin-type heteropolyacid, which demonstrate that the introduction of TEA can improve the photocatalytic activity.Display Omitted
Keywords: Polyoxometalates; 1D chain structures; Keggin; Photocatalytic hydrogen evolution;

The chemical preparation, crystal structure and spectroscopic characterization of the novel noncentrosymmetric (S)nicotiniumtrichloridozincate monohydrate complex are reported. The atomic arrangement can be described as built up by chains of ZnNCl3 tetrahedra and water molecules, interconnected via O–H…Cl hydrogen bonds. The organic entities are inserted between these chains through C–H…Cl and N–H…Cl hydrogen bonds. The 3D Hirshfeld surfaces and the associated 2D fingerprint plots were investigated for intermolecular interactions. The 13C and 15N CP-MAS NMR spectra are in agreement with the X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed the attribution of the NMR peaks.Display Omitted
Keywords: Trichloridozincate; X-ray diffraction; Intermolecular contacts; Quantum calculations; NMR; DFT calculations;

Oxidation of a dimethyl platinum(II) complex with xenon difluoride: The important role of solvent by Anwar Abo-Amer; Paul D. Boyle; Richard J. Puddephatt (193-196).
The oxidation of [PtMe2(bu2bipy)] with XeF2 in dichloromethane or acetonitrile solution has given crystals of trans-[PtFClMe2(bu2bipy)] or trans-[PtF{NHC(=O)Me}ClMe2(bu2bipy)] respectively, but none of the expected product [PtF2Me2(bu2bipy)]. It is suggested that the initial reaction occurs with solvent participation to give xenon and trans-[PtF(S)Me2(bu2bipy)]+  F, S = solvent. When S = CH2Cl2, this is followed by rapid nucleophilic attack by fluoride on the coordinated solvent to give trans-[PtFClMe2(bu2bipy)] and CH2FCl, but, when S = MeCN, by slow hydrolysis to give trans-[PtF{NHC(=O)Me}Me2(bu2bipy)] and HF. The evidence is based on monitoring of the reactions by 1H and 19F NMR spectroscopy in CD2Cl2 or CD3CN solvent. The mechanistic conclusions are significant in the context of the current interest in the use of XeF2 as a reagent in C–F and C–C coupling reactions.In contrast to most precedents, the oxidation of [PtMe2(bu2bipy)] by XeF2 occurs with trans stereochemistry and involves a solvent molecule CH2Cl2 or MeCN in forming the products trans-[PtFClMe2(bu2bipy)] or trans-[PtF{NHC(=O)Me}ClMe2(bu2bipy)].Display Omitted

Metal-centered oxidation decreases nitrile hydration activity of bioinspired (N2S3)Ru-PPh3 precatalysts by Davinder Kumar; Mark S. Mashuta; Craig A. Grapperhaus (197-199).
A series of ruthenium(II) nitrile hydration catalysts based on the pentadentate ligand 4,7-bis(2′-methyl-2′-mercaptopropyl)-1-thia-4,7-diazacyclononane and its sulfur-oxidized derivatives has been oxidized at the metal center yielding their ruthenium(III) counterparts. Metal-centered oxidation results in complete loss of nitrile hydration activity for the dithiolato (RS/RS) parent complex. The sulfur-oxidized thiolato/sulfinato (RS,RSO2 ) derivative displays a decrease in turnover number from 238 ± 23 to 3 ± 1 upon oxidation of Ru(II) to Ru(III). A similar decrease in turnover number from 242 ± 23 to 7 ± 3 is observed upon metal-centered oxidation of the sulfenato/sulfinato (RSO, RSO2 ) derivative. The inactive complex [(4,7-bis(2′-methyl-2′-mercaptopropyl)-1-thia-4,7-diazacyclononane)(triphenyl-phosphine)ruthenium(III)]hexafluorophosphate has been synthesized and characterized by electronic spectroscopy, electron paramagnetic resonance, and single crystal X-ray diffraction studies.Display Omitted
Keywords: Ruthenium; Metal-oxidation; Sulfur-oxidation; Nitrile hydration; Nitrile hydratase;

Reported herein are two porous interpenetrated anionic Cd-carboxylate frameworks tuned by the length of organic linker. Shorter BDC linker and [Cd(COO)4] building blocks in 1 generate a rare 4-connected 2-fold interpenetrating qtz network. But longer NDC linker in 2 produces a self-penetrated 8-connected bcu framework with [Cd3(COO)8] SBUs. 1 and 2 both show selective CO2 adsorption and significantly, 2 exhibits the highest water vapor uptake performance (281 cm3·g− 1 at 298 K and P/P0  = 0.95) among all the interpenetrated MOFs.The bulk of linkers introduced to two 3D interpenetrated porous Cd-MOFs exhibiting 2-fold interpenetrated qtz and self-penetrated bcu nets, which have selective CO2 uptake and highest water vapor uptake performance among all the interpenetrated MOFs.Display Omitted
Keywords: MOFs; Interpenetrated nets; CO2 adsorption; Water vapor uptake;

Unsymmetrical cyrhetrenyl and ferrocenyl azines derived from 5-nitrofurane: Synthesis, structural characterization and electrochemistry by Johana Gómez; A. Hugo Klahn; Mauricio Fuentealba; Diego Sierra; Claudio Olea-Azar; Manuela E. Medina (204-206).
A new series of unsymmetrical cyrhetrenyl and ferrocenyl azines that were monosubstituted [(η5-C5H4)–C(R)=N–N=CH(5-NO2–2-C4H2O)]M {with M=Re(CO)3 and R=H (1a) or R=Me (1b); M=Fe(η5-C5H5) and R=H (2a) or R=Me (2b)} and disubstituted [Fe{(η5-C5H4)–C(Me)=N–N=CH(5-NO2–2-C4H2O)}2] (3a) were prepared by condensation reactions of the corresponding organometallic hydrazone [(η5-C5H4)–C(R)=N–NH2)]M with 5-nitro-2-furaldehyde. The 1H and 13C{1H} NMR spectra indicated that these compounds adopted an (E,E)-configuration about the ˃C=N − bond and an s-trans conformation about the N1–N2 bond, and this result was confirmed by X-ray crystallographic analyses of 1a and 2b. The opposite electronic effects of the organometallic fragments correlate with the co-planarity of the [(η5-C5H4)–C(R)=N–N=CH(5-NO2–2-C4H2O)] system, the reduction potential of the nitro group (E 1/2) and the chemical shifts of the iminic carbons.A new series of unsymmetrical cyrethrenyl and ferrocenyl azines monosubstituted and disubstituted derived from 5-nitrofurane have been prepared. They adopted an (E,E)-configuration in solution and in the solid stateas confirmed by X-ray structures of 1a and 2b.Display Omitted
Keywords: Cyrhetrenyl azines; Ferrocenyl azines; Nitrofurane; Crystal structure; NMR; Cyclic voltammetry;

Reduction of CO2 to methanol using aluminum ester FLPs by Nathan C. Smythe; David A. Dixon; Edward B. Garner; Meredith M. Rickard; Mariano Mendéz; Brian L. Scott; Barbara Zelenay; Andrew D. Sutton (207-209).
Herein we report the synthesis of Al-based esters containing halogenated benzene rings. These Lewis acids were paired with phosphines to form frustrated Lewis pairs (FLPs) which could subsequently bind CO2. While these FLPs were not sufficiently water-stable to catalyze the reduction of CO2 to MeOH using NH3BH3 as the reductant, we examine the effect of varying Lewis acid strength.Frustrated Lewis pairs (FLPs) are combinations of Lewis acids and Lewis bases where the acid and base are either sterically or geometrically restricted from interacting as strongly as their electronic structures would allow. This effect leads to enhanced reactivity towards small molecules and, consequently, interest in their potential as metal-free catalysts [1–5]. To-date, the biggest success has been based around the ability of a myriad of systems to heterolytically cleave H2 and perform catalytic hydrogenations [2,3].
Keywords: Frustrated Lewis pair;; CO2;; MeOH;; Ammonia borane;

Synthesis and X-ray structural characterization of square-pyramidal copper(II) complex with aminoguanidine derivative by Geziel R. Andrade; Jéssica Kunsminskas; Lucas Pizzuti; Ademir dos Anjos; Simone D. Inglez; Bárbara Tirloni; Patrícia H. Suegama (210-213).
Aminoguanidine and its derivatives have shown antiglycation activity and are effective antioxidants. Complexes with ligands derived from aminoguanidine are relevant to both medicinal and bioinorganic chemistry. In this article, we describe the synthesis and characterization of a new mononuclear complex of copper(II) with a chelating ligand derived from aminoguanidine. Single crystals of the resulting complex were obtained by recrystallization from isopropanol. The molecular structure of the complex was obtained by X-ray diffraction which shows a distorted square pyramidal geometry, where copper(II) is coordinated to four nitrogen atoms (base of the pyramid) and to one chlorine atom (pyramid peak). The spectroscopic behavior (FT-IR and UV–vis) of both the complex and the ligand were examined.The molecular structure of the complex of copper(II) (left) and pseudo-polymer (right).Display Omitted
Keywords: Aminoguanidine derivatives,; Copper(II) complex,; X-ray structural characterization;

Synthesis and structures of monocyclic 1,4-diaza-2,3-diborine species by H. Can Söyleyici; Sultan Uyanık; Resul Sevinçek; Erkan Fırıncı; Banu Bursalı; Osman Burgaz; Muhittin Aygün; Yüksel Şahin (214-216).
New monocyclic 1,4-diaza-2,3-diborine derivatives 3ad, 3ae and 3bc and bicyclic 1,4-diaza-2,3-diborine 8a were prepared by reacting 1,4-diaza-2,3-diene dianion (5) with 1,2-dichlorodiborane (6) and 1,2-dichloro-1,2-diborolane (7). The structures of these new derivatives, which are likely ligands for metal complexes, have been characterized by nuclear magnetic resonance (NMR). The crystal structures of 3ad and 3bc have been determined by single crystal X-ray diffraction technique. In the crystal structure of 3ad, the asymmetric unit contains one-half of the molecule, with the other half generated by (x,y,3/2-z) symmetry operation. Considering the X-ray crystallographic results of these compounds, the B–B bonds are typical for single bonds, with the bond lengths of 1.700 and 1.697 Å. Optimized geometric results and Natural Bond Orbital analysis also endorsed that these bond types are single bonds. In 3ad, diazadiborine ring is almost planar, while this ring is in half-chair conformation in 3bc. These compounds, although many aminoboranes are stable in air, were observed not to be stable in air. They have also shown non-aromatic characteristics.In these work, we reported the synthesis and characterization of new monocyclic 1,4-diaza-2,3-diborine derivatives 3ad, 3bc, 3ae and a new bicyclic 8a that may have ligand properties characteristic of metals. For the first time, their x-ray, NICS and NBO analyses were carried out, consequently revealing their nonaromatic characteristics.New monocyclic 1,4-diaza-2,3-diborine derivatives were synthesized and characterized. These structures were examined in detail by single crystal X-ray diffraction technique and NMR spectra.Display Omitted
Keywords: Diazadiborine; Borazine; Heterocycles with BN-moieties; Natural bond orbital analysis;

Two Co(II) coordination polymers, formulated as [Co(bix)(tbta)] n (1) and [Co(bix)0.5(aip)(H2O)] n (2) (bix = 1,4-bis(imidazol-1-ylmethyl)benzene, H2tbta = tetrabromoterephthalic acid, H2aip = 5-aminoisophthalic acid) have been synthesized and structurally characterized by single crystal X-ray diffraction. Complex 1 features a 3D three-fold interpenetrating diamond framework. Complex 2 is a 2D (3,4) network with 3,4L83 topology and extend into an unusual (5,6)-connected 3D supramolecular framework via intermolecular hydrogen bonds. In addition, fluorescence and catalytic performances of complexes 1 and 2 for the degradation of Congo red dye in a photo-Fenton-like process were investigated.Two new Co(II) coordination polymers based on bis(imidazole) and different dicarboxylates were synthesized and characterized structurally. Compound 1 exhibits a three-fold interpenetrating dia architecture, compound 2 shows a 2D (3,4)-connected 3,4L83 network, which is further extended into an unprecedented (5,6)-connected 3D supramolecular framework by hydrogen bond interactions. Both two complexes exhibit catalytic activities for the degradation of the Congo red dye in a photo-Fenton-like process.Display Omitted
Keywords: Bis(imidazole); Catalysis; Coordination polymer; Cobalt(II); Dicarboxylate anion;

We report the synthesis of a novel bis-pyridine chelate derived from an anthracene scaffold. Complexation of the N2 ligand with rhenium carbonyl affords the Re tricarbonyl bromide complex [(Anth-N2)Re(CO)3Br]. In THF solution, the title complex exhibits two quasi-reversible reductions located near − 2.1 and − 2.5 V vs Fc/Fc+, which are similar to those observed in the free Anth-N2 ligand, suggesting the non-innocent behavior of the complexed anthracene scaffold. Under CO2 atmosphere, the title complex exhibits an electrocatalytic response consistent with CO2  → CO reduction, and the presence of electrocatalytically generated CO was confirmed by bulk electrolysis. These results suggest that alternate locations of redox activity (other than at the Re metal center, pyr donors, or bpy framework) can lead to interesting electrochemical behavior.Display Omitted
Keywords: Rhenium; Electrochemistry; Redox; Scaffold; X-ray; NMR;

The hydrothermal reaction of CoF2 and 4,4′,4″,4″’-(porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid) (H6tcpor) provides a mixture of crystalline products, including H2porph, [Co(porph)] (H2porph = C20H14N4), and [Co(H2O)3{Co(H3tcpor)}2{Co(H4tcpor)}]·4H2O (1·4H2O). Due to the small size, weak diffraction and intergrowth nature of the crystals, the identities of the products were determined using synchrotron single crystal X-ray diffraction. The title compound 1·4H2O is a tetranuclear cluster of Co(II) sites. Two {Co(H3tcpor)}1 − and one {Co(H4tcpor)} subunits radiate from the central {Co(H2O)3}2 + moiety of the cluster. Hydrogen bonding stabilizes the central {Co(H2O)3(O2C–)2(HO2C–)} core as well as providing extensive three dimensional connectivity between the cluster units.Hydrothermal synthesis provided small crystals of the tetranuclear Co(II)complex [Co(H2O)3{Co(H3tcpor)}2{Co(H4tcpor)}], whose structure was determined by synchrotron X-ray diffraction.Display Omitted
Keywords: Metalloporphyrin cluster; Synchrotron X-ray diffraction; Tetranuclear cobalt(II) cluster; Hydrogen bonding;

A new bimetallic Ru(II) complex bridged by (Z)-1-(4-fluorobenzyl)-3-((4-fluorophenyl)(3H-pyrrolo[3,4-f]isoquinolin-3-ylidene)methyl)-2H-pyrrolo[3,4-f]isoquinoline has been synthesized and characterized by electronic spectroscopy, 1HNMR, HRMS, and elemental analysis. Binding studies with calf thymus DNA (ctDNA) show binding constants as high as 105  M− 1 indicating a strong interaction of the complex with DNA. When aqueous solutions of the complex and plasmid DNA are irradiated with low energy light for brief periods of time, complete photocleavage of the DNA is observed.A new bimetallic ruthenium(II) complex has been synthesized. Photolysis of aqueous solutions of circular DNA in the presence of the ruthenium complex indicates double strand breaks of DNA.Display Omitted
Keywords: Dinuclear ruthenium; Photodynamic therapy; Dipyrromethane;