Inorganic Chemistry Communications (v.52, #C)

Contents List (iii-viii).

Reaction of NiII acetate and 4-methylphthalic acid (H2mph) with 1,2-bis(4-pyridyl)ethane (bpa) or 1,2-bis(4-pyridyl)ethene (bpe) affords two 3-D unusual metal–organic frameworks {[Ni(Hmph)2(bpa)(H2O)2][Ni2(mph)2(bpa)3]} n (1) and [Ni2(mph)2(bpe)2(H2O)3] n (2). 1 represents a polythreaded supramolecular architecture consisting of distinct 1-D armed chains and 2-D sql sheets based on the binuclear [Ni2(mph)2] units, however, 2 shows a rare 3-fold interpenetrating 103-ths network.Assembly of NiII salt and 4-methylphthalic acid with bpa or bpe affords two complexes. The significant difference between 1 and 2 isolated under the same conditions must be ascribed to the nature of N-donor auxiliary ligands.Display Omitted
Keywords: NiII-MOFs, 4-methylphthalic acid; 1,2-Bis(4-pyridyl)ethane; 1,2-Bis(4-pyridyl)ethane; Magnetic properties;

Facile synthesis, electronic structure and photocatalytic activity of a novel Bi-based hydroxyl oxalate Bi(C2O4)OH by Ke Xiao; Na Tian; Yuxi Guo; Hongwei Huang; Xiaowei Li; Yihe Zhang (5-8).
A novel Bi-based hydroxyl oxalate Bi(C2O4)OH has been successfully synthesized via a facile aqueous precipitation route, and its photocatalytic activity was investigated for the first time. The as-prepared Bi(C2O4)OH nanorods were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis diffuse reflectance spectra (DRS) and photoluminescence (PL) spectra. It possesses an indirect-transition optical band gap of 3.73 eV. The electronic structure, density of states as well as light absorption of Bi(C2O4)OH were studied by the first principle calculations. The photocatalytic performance of the samples was determined by photodegradation of Rhodamine B (RhB) in aqueous solution. The results revealed that RhB can be effectively decomposed by Bi(C2O4)OH, and the sample with reactant molar ratio of 1:2 exhibits the highest photocatalytic activity. The active species trapping experiments over Bi(C2O4)OH indicated that the hydroxyl radicals (•OH) are the most important active species in the process of RhB photodegradation.A novel Bi-based hydroxyl oxalate Bi(C2O4)OH has been successfully synthesized via a facile aqueous precipitation route, and its photocatalytic activity was investigated for the first time.Display Omitted
Keywords: Bi(C2O4)OH; Photocatalysis; Band gap; Electronic structure; RhB;

Structure and photocatalytic property of a new Cu(II) based framework with jsm topology by Bo Xu; Zhiming Chen; Pengfei Zhi; Guangning Liu; Cuncheng Li (9-11).
A new coordination polymer [Cu(mip)(bpy)0.5]n (1) was obtained through reaction of 5-methylisophthalic acid (H2mip) and 4,4′-bipyridine (bpy) with copper nitrate under hydrothermal condition. X-ray single crystal diffraction analysis reveals that complex 1 exhibits a 3D network with jsm topology. Photocatalytic activity of the complex has also been characterized. Notably, complex 1 represents the rare example of visible-light-driven photocatalyst based on coordination polymer and shows good degradation ability over methylene blue (MB).A new Cu(II)-based coordination polymer exhibiting a 3D network with jsm topology and showing interesting degradation ability over methyl blue is reported.Display Omitted
Keywords: Coordination polymer; Crystal structure; Photocatalytic activity;

A novel coordination polymer, namely, [Cd7(4,4′-tmbpt)3(d-cam)6(OH)2]·8.25H2O (1), where 4,4′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(4-pyridyl)-1,2,4-triazole, and d-H2cam =  d-camphoric acid, has been synthesized under hydrothermal condition. Compound 1 exhibits a three-dimensional homochiral (3,8,9)-connected framework, which is a rare example of coordination polymer with homochiral highly connected structure based on the chiral source of d-H2cam. The structure of the compound was determined by single-crystal X-ray diffraction analysis and further characterized by infrared spectrum (IR), elemental analysis and UV–Vis spectrum. Moreover, the optical band gap and photoluminescent property of the compound have been investigated.A novel coordination polymer with chiral highly connected structure has been prepared under hydrothermal condition, where its optical band gap and photoluminescent property have also been studied.Display Omitted
Keywords: Coordination polymer; Chiral; Highly connected; Band gap; Photoluminescence;

Three new two-dimensional coordination polymers were constructed from 2,6-bis(imidazole-1-yl)pyridine (2.6-bip), terephthalic acid (1,4-bdcH2), and M(NO3)∙nH2O (M = Co, Cd). [M(2,6-bip)(1,4-bdc)] (1: M = Co; 2: M = Cd) were prepared under hydrothermal condition, whereas [Cd(2,6-bip)(1,4-bdc)∙xDMF] (3) was obtained under solvothermal condition in DMF solvent. Single-crystal X-ray analyses revealed the first example of a 2D 4-connected net of 66 topology in 1 and 2 and a rare 2D 4,5-connected net of 4,5 L20 topology in 3. All these complexes were thermally robust and emissive in solid-states. This work confirmed the versatility of using hingelike 2,6-bip as a linker and the importance of solvent effect in the process of framework formation.Three new two-dimensional coordination polymers are presented. [M(2,6-bip)(1,4-bdc)] (1: M = Co; 2: M = Cd; 2,6-bip = 2,6-bis(imidazole-1-yl)pyridine; 1,4-bdc = 1,4-benzenedicarboxylate) exhibit the first example of a 2D 4-connected net of 66 topology. The framework in [Cd(2,6-bip)(1,4-bdc)∙xDMF] (3) is a rare 4,5-connected net of 4,5 L20 topology.Display Omitted
Keywords: Crystal structure; 2,6-Bis(imidazole-1-yl)pyridine; Cadmium; Cobalt; Net topology;

A new three-dimensional lanthanide–manganese metal–organic framework [Gd2Mn3(PZTC)4(H2O)12]·5H2O (PZTC = 2,3,5-Pyrazinetricarboxylate) has been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, and X-ray diffraction. Single-crystal X-ray diffraction shows that Gd3 + and Mn2 + ions are linked together to form a porous 3D Gd–Mn MOF by the alternative arrangement of two kinds of PZTC3 − ligands. Taking the Gd, Mn and PZTC as node, the Schläfli symbol of the topology can be expressed as {4;82}2{42;6}2{42;84}2{43;6;84;102}2{8}. Magnetic study indicates the magnetic coupling between two Mn2 + ions through double monatomic carboxylate–oxo bridges is weak antiferromagnetic, while that between Gd3 + and Mn2 + ions through the carboxylate group in synanti-bridging mode is negligible.A new three-dimensional lanthanide–manganese metal–organic framework [Gd2Mn3(PZTC)4(H2O)12]·5H2O (PZTC = 2,3,5-pyrazinetricarboxylate) with a topology of {4;82}2{42;6}2{42;84}2{43;6;84;102}2{8} was described. The magnetic coupling between two Mn2 + ions through double monatomic carboxylate–oxo bridges is weak antiferromagnetic, while that between Gd3 + and Mn2 + ions through the carboxylate group in synanti-bridging mode is negligible.Display Omitted
Keywords: Heterometallic coordination polymer; Crystal structure; 2,3,5-Pyrazinetricarboxylate; Magnetism;

Synthesis, crystal structure and photoluminescent properties of a 3D Zn(II) coordination polymer by Xiao-Nan Zhang; Xiao-Man Cao; Miao Hao; Bei-Bei Kang; Ming-Liang Gao; Zheng-Bo Han (23-26).
A new 3D coordination polymer [NH2(CH3)2]2[Zn7L4(DMF)2(H2O)3]·19H2O (1) (L = 2,3′,5,5′-biphenyl tetracarboxylic acid) has been solvothermally synthesized and structurally characterized by IR, elemental analysis and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicate that 1 exhibits 3D framework with a one-dimensional (1D) channel. The luminescence properties have been studied, and the results showed that 1 displays strong fluorescent emissions both in the solid state and in methanol suspension at room temperature. More interesting, the addition of Fe3 + causes the fluorescence intensity of 1 to be weakened, which implies that it may be used as luminescent probes of Fe3 +.Display Omitted
Keywords: Metal–organic frameworks; Crystal structure; Photoluminescence properties; Luminescent probe;

Synthesis, structure, stability and DNA cleavage activities of three Cr(III) complexes with salicylate and ammonium ligands by Bin Liu; Jie Chai; Xiangquan Hu; Yujiao Zhang; Junxia Nan; Binsheng Yang (27-30).
Complexes [Cr(III)(SA)(en)2]+ (1), [Cr(III)(SA)(DETA)(H2O)]+ (2) and [Cr(III)(SA)(TETA)]+ (3) were synthesized (H2SA = salicylic acid, en = ethylenediamine, DETA = diethylenetriamine, TETA = triethylenetetramine). Kinetics studies show that 2 is the most instable one among these complexes. In addition, only 2 is found to be a very efficient catalyst of the cleavage of PBR322 DNA in the absence of any added cofactor. The degradation rate from supercoiled form to nicked form was 1.05 ± 0.081 h− 1 (10− 5  M) at pH 7.4 and 37 °C. Thiobarbituric acid-reactive substances assay shows 2 fail to produce •OH causing any degradation of deoxyribose ring even in the presence of ascorbic acid. Ethidium bromide displacement assay suggests that only 2 can kick out EB from the groove of DNA. The interaction with DNA causes a blue shift of the d → d transition spectra of 2.Salicylate chromium(III) complex with diethylenetriamine ligand [Cr(III)(SA)(DETA)(H2O)]+ (2) can efficiently cleavage of PBR322 DNA in the absence of any added cofactor.Display Omitted
Keywords: Chromium(III); Salicylate; Ammonium; DNA cleavage; Hydrolysis;

New experimental insights into the formation of unexpected water-soluble Eu(III)–Cu(II) 15-metallacrown-5 compound with acetate by Marina A. Katkova; Galina S. Zabrodina; Maria S. Muravyeva; Alexandr A. Khrapichev; Maxim A. Samsonov; Georgy K. Fukin; Sergey Yu. Ketkov (31-33).
Despite a large amount of systematic structural studies of the affinity of copper–lanthanide 15–metallacrown-5 complexes derived from α-aminohydroxamic acids for various organic carboxylates, the acetate ion has not been previously observed to bind to the Ln3 +[15-MC-5]. The first Eu(OOCCH3)[15-MCCu(II)Glyha-5](NO3)2 metallacrown with acetate coordinating to the central lanthanide ion has been prepared in 75% yield. According to the X-ray diffraction study all bond distances and angles in this complex are in the ranges typical for metallacrowns. However, due to a specific network of hydrogen bonds the coordination of the acetate anion to the Eu[15-MCCu(II)Glyha-5]3 + cation leads to a greater distortion of the metallacrown cation from planarity as compared to the known nitrate analogues.The first example of acetate lanthanide 15-metallacrown-5 derivative Eu(OOCCH3)[15-MCCu(II)Glyha-5](NO3)2 has been prepared and structurally characterized by single-crystal X-ray diffraction.Display Omitted
Keywords: Europium; Copper; Metallacrown; X-ray structure;

Two coordination polymers {[Cu4(OH)2(btrb)2(btc)2]·4H2O}n (1) and {[Cd2(btrb)(adc)2(H2O)]·H2O}n (2) were synthesized with hydrothermal method and characterized (btrb = 1,4-bis(1,2,4-triazol-4-ylmethyl)benzene, btc = 1,3,5-benzenetricarboxylate, adc = 1,3-adamantanedicarboxylate). 1 shows an unusual (3,10)-connected two-dimensional metal–organic framework based on the tetranuclear copper(II) cluster [Cu43-OH)2]. 2 is an interesting three-dimensional network based on the one-dimensional metal–organic nanotube. 1 shows good photocatalytic activity for the degradation of methyl blue (MB). The luminescence of 2 was investigated.Two coordination polymers {[Cu4(OH)2(btrb)2(btc)2]·4H2O}n (1) and {[Cd2(btrb)(adc)2(H2O)]·H2O}n (2) were synthesized and characterized. 1 shows an unusual (3,10)-connected 2D metal–organic framework based on the tetranuclear copper(II) cluster [Cu43-OH)2]. 2 is an interesting 3D network based on the 1D metal–organic nanotube. 1 shows good photocatalytic activity for the degradation of methyl blue (MB). The luminescence of 2 was investigated.Display Omitted
Keywords: Coordination polymer; Tetranuclear copper(II) cluster; Photocatalysis; Bis(1,2,4-triazol-4-ylmethyl)benzene;

Two pyrene derivatives were prepared by the condensation between diaminomaleonitrile and 1-pyrene-aldehyde or 2-pyrene-aldehyde. Both of them exhibit high selectivity for Cu2 + and ClO in combination with significant fluorescence enhancement in certain buffer solutions, respectively.Display Omitted
Keywords: Chemosensor; Pyrene; Diaminomaleonitrile; Copper(II); Hypochlorite;

Through changing the components of solvent, two Mg-based metal–organic frameworks were synthesized, which possess the same two-fold interpenetrated ReO3 net constructed by identical linkers, 4,4′,4″-benzene-1,3,5-triyl-tribenzoate, but distinct nodes, Mg2 and Mg6 units, respectively. Here, DMSO and water are key factors for forming hexanuclear clusters, while DMF and DMSO act as template reagents for constructing super-octahedral cavities.Through changing the components of solvent, two Mg-based metal–organic frameworks are synthesized, which present the same two-fold interpenetrated ReO3 nets constructed by identical linkers, 4,4′,4″-benzene-1,3,5-triyl-tribenzoate, but distinct nodes of Mg2 and Mg6 units, respectively.Display Omitted
Keywords: Metal–organic framework; ReO3 net; Magnesium-containing cluster; Solvent effects;

Magnetic properties of Mg/Co(II)–Al/Fe(III) layered double hydroxides by Qiuhang Li; Lei Xing; Xianwei Lu; Na Li; Mingxiang Xu (46-49).
Mg/Co–Al/Fe–CO3 layered double hydroxides were synthesized by coprecipitation reaction method. According to powder X-ray diffraction (Cu–Kα) and scanning electron microscopy, all the samples exhibit hydrotalcites with layered double structure. Onefold Co2 + or Fe3 + doping does not show ferromagnetism. Room temperature ferromagnetism can be obtained by Co2 + and Fe3 + codoping, on the condition that more than 50% of Mg2 + and Al3 + are substituted by Co2 + and Fe3 +, respectively. The coaction of different magnetic interactions leads the macroscopic ferromagnetism of the samples. The ferromagnetic coupling of Co2 +–O2−–Co2 + results in the ferromagnetism of brucite-like layers and the antiferromagnetic coupling of Co2 +–O2−–Fe3 + enhances the magnetism of the interlayers.Display Omitted
Keywords: Layered double hydroxides; Coprecipitation; Magnetic property; Room temperature ferromagnetism;

A new UiO-66-type zirconium metal organic framework material UiO-66(AN) was prepared by using chromophoric anthracene-9,10-dicarboxylic acid as linker. The large-sized conjugate π-system in the ligand results in the bathochromic shift of the absorption peaks into the visible light region in the absorption spectrum of UiO-66(AN), compared to those of UiO-66 and analogs UiO-66(NA) made of terephthalate and naphthalene-1,4-dicarboxylic acid, respectively. UiO-66(AN) was shown to be an efficient photocatalyst for degradation of methyl orange. Our finding shows promises for the development of more efficient MOFs as photocatalysts by using chromophoric conjugate ligands.A new UiO-66-type metal–organic framework UiO-66(AN) was synthesized by using anthracene-9,10-dicarboxylic acid as linker, which showed enhanced photocatalytic activity for degradation of methyl orange in comparison with the UiO-66 and analogs UiO-66(NA) made of terephthalate and naphthalene-1,4-dicarboxylic acid, respectively.Display Omitted
Keywords: MOFs; Zirconium; UiO-66 analogs; Photocatalysis; Degradation of methyl orange;

PMMA-supported hybrid materials doped with highly near-infrared (NIR) luminescent neutral trikis-β-diketonate Yb3 + complex by Zhao Zhang; Lin Liu; Chao Yu; Hongyan Li; Yani He; Xingqiang Lü; Wai-Kwok Wong; Richard A. Jones (53-55).
Based on self-assembly of a trifluorinated and acylpyrazole-modified β-diketonate ligand HL ((Z)-3-methyl-1-phenyl-4-(2,2,2-trifluoro-1-hydroxyethylidene)-1H-pyrazol-5(4H)-one), LnCl3⋅ 6H2O (Ln = La, Yb or Gd) and 2,2′-bpy (2,2′-bipyridine), three trikis-β-diketonate complexes [Ln(L)3(2,2′-bpy)] (Ln = La, 1; Ln = Yb, 2 or Ln = Gd, 3) were obtained, respectively. Further through physical doping, the series of PMMA-supported hybrid materials PMMA@[Ln(L) 3 (2,2′-bpy)] with high thermal stability and good film-forming property are obtained. Especially for PMMA@2, the doping also causes the improved NIR luminescent property (Φem  = 0.97%) in comparison to the individual Yb3 +-β-diketonate complex 2 (Φem  = 0.81%) even up to a concentration of 200:1.In the obtained PMMA-supported doping hybrid materials PMMA@[Yb(L) 3 (2,2′-bpy)], besides the improvement of thermal stability and film-forming property, the doping causes the improved NIR luminescent property (Φem  = 0.97%) in comparison to the individual Yb3 +-β-diketonate complex 2 (Φem  = 0.81%) even up to a concentration of 200:1.Display Omitted
Keywords: PMMA-supported Yb3 +-based doping hybrid materials; Trifluorinated and acylpyrazole-modified β-diketonate; Energy transfer;

The coordination chemistry of the ligand precursor 1-benzoyl-4,5-dihydro-3,5-bis(trifluoromethyl)-1H-pyrazol-5-ol (1a) to iron(II) acetate was studied. In dependence of the added co-ligand different complex geometries were observed. In case of 4-dimethylaminopyridine (DMAP) as co-ligand an octahedral iron(II) complex was found with an O,N,O′-coordination of the tridentate ligand (1a-2H), in which the ligand is planar, the oxygen donors are trans to each other, and the nitrogen donor is in a cis position. The other coordination sites on the iron center are occupied by DMAP ligands. In contrast to that, with triphenylphosphane as the co-ligand an oxidation process took place, which revealed an octahedral iron(III) complex with a comparable geometry for the tridentate ligand (O,N,O′-coordination, 1a-2H) demonstrating the usefulness of 1a-2H to stabilize different oxidation states. The additional coordination sites are occupied by one triphenylphosphane oxide and ethoxide ligands. Interestingly, the ethoxide ligands act as bridging ligands to form a bimetallic complex.Display Omitted
Keywords: Iron; Tridentate ligand; Octahedral geometry; Oxidation states;

Peculiar photoinduced properties of water-soluble, early lanthanide(III) porphyrins by Muhammad Imran; Csanád Szentgyörgyi; Gábor Eller; Zsolt Valicsek; Ottó Horváth (60-63).
Water-soluble, early lanthanide(III) mono- and bisporphyrin complexes possess very similar UV–Vis absorption as well as photophysical and photochemical properties, as a consequence of a special type of aggregation, through the peripheral substituents. In the absence of the bidentate, O-donor acetate ligand, bisporphyrin can form too, which has slightly redshifted and broadened absorption bands, compared to those of the monoporphyrin. Also the bisporphyrin displays a blueshifted and less intense fluorescence, related to the free-base porphyrin. The formation of complexes and the transformation between the mono- and bisporphyrins are very slow reactions in dark at room temperature. These reactions are accelerated by the photolysis of the system, which are considerable by-processes of the photoredox degradation. Depending on the wavelength of irradiation, two types of photoproducts can appear: during the photolysis at the Soret-band, a radical type intermediate can be observed, which disappears in dark. However, during the irradiation at the Q-bands, a new photoproduct appears, which is stable in dark and undetectable in the case of post-transition metal ions' out-of-plane porphyrin complexes.During the photolysis of lanthanide(III) porphyrins at the Soret-band, a radical type intermediate can be observed, which disappears in dark. However, during the irradiation at the Q-bands, a new photoproduct appears, which is stable in dark and undetectable in the case of post-transition metal ions' out-of-plane porphyrin complexes.Display Omitted
Keywords: Out-of-plane metalloporphyrins; Early lanthanide(III) ions; Tail-to-tail oligomerization; LMCT; Charge separation; Water cleavage;

A crystal structure of a compartmental ligand N,N′-bis(2,3-dihydroxybenzylidene)-1,3-diaminopropane (H4L = C17H18N2O4) (1) containing N2O2-inner and O4-outer coordination sites and a characterization of its novel diphenoxo-bridged discrete dinuclear complex [CuDy(H2L)(MeOH)(NO3)3]·2MeOH (2) are reported. The Schiff base ligand 1 crystallizes in the orthorhombic P212121 space group with a molecule in a bent conformation. The compound at 100 and 293 K displays the keto-enol tautomerism with the equilibrium in both temperatures shifted with a different degree towards the zwitterionic keto-amino form. The quantum chemical calculations showed preferences for enol-imino form in a gas phase and for keto-amine in solutions. The keto-amino tautomer is stabilized by intermolecular interactions. The complex 2 crystallizes in the triclinic P-1 space group as a dinuclear compound with CuIIDyIII core. The Dy(III) ion is nine-coordinated whereas the coordination number of Cu(II) is five. The temperature dependence of the magnetic susceptibility and the field-dependent magnetization indicated that the interaction between Cu(II) and Dy(III) metal centers in 2 is ferromagnetic.The structure of N,N′-bis(2,3-dihydroxybenzylidene)-1,3-diaminopropane (H4L = C17H18N2O4) (1) was determined. The keto-enol tautomerism of the hexadentate Schiff base ligand was studied at 100 and 293 K. A new diphenoxo-bridged [CuDy(H2L)(MeOH)(NO3)3]·2MeOH complex (2) that crystallizes in the triclinic P-1 space group was synthesized. In this compound 3d and 4f metal centers are ferromagnetically coupled.Display Omitted
Keywords: Schiff base; Tautomerism; 3d–4f complex; Ferromagnetic interaction;

Assembly of two Cu-based coordination polymers from 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylate ligand by Cong Dai; Xiaoying Zhou; Xuemin Jing; Guanghua Li; Qisheng Huo; Yunling Liu (69-72).
Two novel Cu-based coordination polymers [Cu5(HPyImDC)4]·(NH4)3 (1) and [Cu3(H2O)2(HPyImDC)2(C3N2H10)] (2) containing the 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylate (H3PyImDC) ligand have been solvothermally synthesized. Single crystal X-ray diffraction analysis reveals that compound 1 exhibits a three dimensional framework with 1D rhombic channels, which can be simplified into a novel (3, 4)-connected network with Schläfli symbol of (62.144)(62.8)4. Compound 2 is one dimensional chain which packed with each other via π–π and hydrogen-bonding interactions to construct a three dimensional supramolecular structure. As the first example related to Cu (I) and Cu (I, II) coordination polymers based on H3PyImDC ligands, compounds 1 and 2 are further studied by elemental analyses, IR spectroscopy and thermogravimetric analyses.Structural views of the two coordination polymers [Cu5(HPyImDC)4·(NH4)3] (1) and [Cu3(H2O)2(HPyImDC)2(C3N2H10)] (2). Compounds 1 and 2 as the first example related to Cu (I) and Cu (I, II) coordination polymers based on H3PyImDC ligands are both constructed from 1D rhombic chains. Compound 1 exhibits a three dimensional framework, and compound 2 is constructed by 1D chains via hydrogen-bonding interactions to form 3D supramolecular structure.Display Omitted
Keywords: Coordination polymer; 2-(Pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid; Three dimensional framework; Supramolecular structure;

White-light generation and full-color in single-phase garnet-based phosphors by Mengmeng Shang; Jian Fan; Yang Zhang; Hongzhou Lian; Jun Lin (73-76).
Presently considerable interest in single-phase white-emitting for ultraviolet light-emitting diodes is stimulated. Here we report the effective single-phase phosphors based on YAG-garnet structure, which exhibit varied hues from blue through white and eventually orange by tuning the relative proportion of Ce3 +/Mn2 + excited at ultraviolet.White-light generation and full-colors were obtained in single-phase garnet-based Y3Al5 − 2x Mg x Si x O12:Ce3 +, Mn2 + (Mg2 +–Si4 + replacing Al(1) 3 +–Al(2) 3 + in garnet-Y3Al5O12 host lattice on octahedron and tetrahedral sites, x = 1 and 2) phosphors using energy transfer principle.Display Omitted
Keywords: Garnet structure; Single-phase phosphors; White light emission; Energy transfer;

Reactions of 1,10-phenanthroline-2,9-dicarboxylic acid (H2phenda) with MnCl2·4H2O or MCl2·6H2O (M = Co, Ni) under solvothermal conditions yielded three octahedral clusters, (H3O)[MnII 66-Cl)(phenda)6]·8MeOH (1·8MeOH), (H3O)[MII 66-Cl)(phenda)6]·6H2O (M = Co, 2·6H2O; M = Ni, 3·6H2O). In the title compounds, the six metal centers are bridged by a μ6-Cl and surrounded by six H2phenda ligands, forming an octahedral cluster. Magnetic studies show that the antiferromagnetic interactions are present in 1·8MeOH, 2·6H2O and 3·6H2O. Moreover, 3·6H2O clearly shows a nonzero out-of-phase χ″ signal with a peak at ca. 11 K, accompanied by a broad one for χ′.Three octahedral clusters of [MII 66-Cl)(phenda)6] (M = Mn or Co or Ni; phenda = 1,10-phenanthroline-2,9-dicarboxylate) have been prepared and characterized. In title compounds, the six metal centers are bridged by a μ6-Cl and surrounded by six H2phenda ligands, forming an octahedral cluster. Magnetic studies show that the antiferromagnetic interactions are present.Display Omitted
Keywords: 1,10-Phenanthroline-2,9-dicarboxylate; Hexanuclear clusters; Magnetic properties;