Different delocalized ranges in mixed valence cyanido-metal-bridged Fe-Ru-Fe complexes controlled by terminal ligand substitution modification.

In order to investigate the properties of metal to metal charge transfer (MMCT) influenced by the relative energy level between the bridging unit and the terminal unit, two groups of heterotrimetallic cyanido-metal-bridged complexes, -[Cp(dppe)Fe-CN-Ru(MeOpy)-NC-Fe(dppe)Cp][X] (1[X]n; = 2, 3, or 4; X = PF or BF) (Cp = cyclopentadiene, dppe = 1,2-bis(diphenylphosphino)ethane, MeOpy = 4-methoxypyridine) and [Cp*(dppe)Fe-CN-Ru(MeOpy)-NC-Fe(dppe)Cp*] [X] (2[X]n; Cp* = 1,2,3,4,5-pentamethylcyclopentadiene; = 2, 3, or 4; X = PF or BF) were synthesized and fully characterized. The crystallography data suggest different oxidation sites in the ground state for one-electron oxidation products 13+ and 23+, and the electrochemical and Mössbauer spectra suggest that in the one-electron oxidation compounds 13+, the charge is delocalized all along the trimetal backbone Fe-Ru-Fe, while in 23+, the charge is rather delocalized between the two metal parts Fe-Ru. Further oxidation of N3+ gives N4+ ( = 1 or 2), during which a spin transfer towards the terminal units is observed in both series.

Metal-Metal Charge Transfer Properties of a Series of Trinuclear Fe Ru and Corresponding Pentanuclear Fe Ru Ag Cyanido-Bridged Complexes.

A series of trimetallic cyanidometal-bridged compounds [Me Cp(dppe)Fe -(μ-NC)-Ru (MeOpy) -(μ-CN)-Fe (dppe)CpMe ] - [PF ] (N[PF ] , n=0, N =1; n=1, N=2; n=3, N=3; Cp=cyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane, MeOpy=4-methoxypyridine) and their one- and two-electron oxidized compounds N and N were synthesized and characterized. Meanwhile, a series of corresponding linear cyanido-bridged pentanuclear compounds [Me Cp(dppe)Fe -(μ-NC)-Ru (MeOpy) -(μ-NC)-Ag -(μ-CN)-Ru (MeOpy) -(μ-CN)-Fe (dppe)CpMe ][BF ] (M[BF ] , n=0, M=4; n=1, M=5; n=3, M=6) were also obtained and well characterized. The investigations suggest that in the trinuclear system there exists remote interaction between the two Fe centers, but no significant interactions exist across the central silver unit between the metals on the two sides of the silver center in the pentanuclear system.

Investigation of the electron transfer properties between metal centers in binuclear and trinuclear cyanido-bridged mixed valence complexes with /-configuration.

To investigate the electron transfer properties between metal centers and their influencing factors in binuclear and trinuclear cyanido-bridged mixed valence complexes with /-configuration, binuclear -[Cp(dppe)Fe(μ-NC)Ru(5,5'-dmbpy)(μ-CN)][PF] (cis-1[PF6]n, = 1, 2) and trinuclear /-[Cp(dppe)Fe(μ-NC)Ru(5,5'-dmbpy)(μ-CN)Fe(dppe)Cp][PF] (cis/trans-2[PF6]n, = 2, 3, 4) (Cp = 1,3-cyclopentadiene, dppe = 1,2-bis(diphenylphosphino)ethane, 5,5'-dmbpy = 5,5'-dimethyl-2,2'-bipyridyl) cyanido-bridged complexes were synthesized and well characterized. The experimental results indicate that the presence of the other terminal fragment Cp(dppe)Fe in cis-2[PF6]4 results in higher MMCT energy than that of cis-1[PF6]2. In addition, the -configuration is more conducive to electron transfer between metal centers than the -configuration in trinuclear cyanido-bridged mixed valence complexes.

FAM83A antisense RNA 1 () silencing impairs cell proliferation and induces autophagy via MET-AMPKɑ signaling in lung adenocarcinoma.

Studies demonstrate that long non-coding RNAs (lncRNAs) play vital roles in cancer progression. However, the expression pattern and molecular mechanisms of lncRNA in lung cancer remain largely unclear. Here, we analyzed expression in lung cancer tissues from three RNA-sequencing (RNA-Seq) datasets and validated these results using quantitative real-time reverse transcription polymerase chain reaction (qRT-PCR) in an independent set of lung adenocarcinoma.

Effects of cis/trans-Configuration and Ligand Substitution of the Cyanidometal Bridge on Metal to Metal Charge Transfer Properties in Mixed Valence Complexes.

To investigate the effects of cis/trans-configuration of the cyanidometal bridge and the electron donating ability of the auxiliary ligand on the cyanidometal bridge on metal to metal charge transfer (MMCT) in cyanidometal-bridged mixed valence compounds, two groups of trinuclear cyanidometal-bridged compounds cis/trans-[Cp(dppe)Fe(μ-NC)Ru(4,4'-dmbpy) (μ-CN)Fe(dppe)Cp][PF ] (n=2 (cis/trans-1[PF ] ), 3 (cis/trans-1[PF ] ), 4 (cis/trans-1[PF ] )) and cis/trans-[Cp(dppe)Fe(μ-NC)Ru(bpy) (μ-CN)Fe(dppe)Cp][PF ] (cis/trans-2[PF ] ) were synthesized and fully characterized. The experimental results indicate that for these one- and two-electron oxidation mixed valence compounds, the trans-configuration compounds are more beneficial for MMCT than the cis-configuration compounds, and increasing the electron donating ability of the auxiliary ligand on the cyanidometal bridge is also conductive to MMCT. Moreover, compounds cis/trans-1[PF ] (n=3, 4) and cis/trans-2[PF ] belong to localized compounds by analyzing the experimental characterization results, supported by the TDDFT calculations.

Influence of Fine Ligand Substitution Modification of the Isocyanidometal Bridge on Metal-to-Metal Charge Transfer Properties in Class II-III Mixed Valence Complexes.

The synthesis and characterization of Class II-III mixed valence complexes have been an interesting topic due to their special intermediate behaviour between localized and delocalized mixed valence complexes. To investigate the influence of the isocyanidometal bridge on metal-to-metal charge transfer (MMCT) properties, a family of new isocyanidometal-bridged complexes and their one-electron oxidation products cis-[Cp(dppe)Fe-CN-Ru(L) -NC-Fe(dppe)Cp][PF ] (n=2, 3) (Cp=1,3-cyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane, L=2,2'-bipyridine (bpy, 1[PF ] ), 5,5'-dimethyl-2,2'-bipyridyl (5,5'-dmbpy, 2[PF ] ) and 4,4'-dimethyl-2,2'-bipyridyl (4,4'-dmbpy, 3[PF ] )) have been synthesized and fully characterized. The experimental results suggest that all the one-electron oxidation products may belong to Class II-III mixed valence complexes, supported by TDDFT calculations.

Tuning metal to metal charge transfer properties in cyanidometal-bridged complexes by changing the auxiliary ligand on the bridge.

In order to investigate the influence of the auxiliary ligand of the cyanidometal bridge on metal to metal charge transfer (MMCT) in cyanidometal-bridged complexes, two groups of heterotrimetallic cyanidometal-bridged complexes, trans-[Cp*(dppe)Fe-NC-Ru(L)2-CN-Fe(dppe)Cp*][PF6]n (L = bpy, 1(PF6)n; L = 4,4'-dmbpy, 2(PF6)n; n = 2, 3, 4) (Cp* = 1,2,3,4,5-pentamethylcyclopentadiene, dppe = 1,2-bis(diphenylphosphino)ethane, bpy = 2,2'-bipyridine, 4,4'-dmbpy = 4,4'-dimethyl-2,2'-bipyridyl) were synthesized and fully characterized. The MMCT of the one-electron oxidation mixed valence complexes is mainly attributed to RuII and FeII → FeIII MMCT transitions, and the MMCT of the two-electron oxidation complexes is mainly attributed to RuII → FeIII MMCT transitions. The energy of the MMCT of the four complexes decreases with the increase of the electron donating ability of the auxiliary ligand of the cyanidometal bridge.

Silencing of impairs cell proliferation and induces autophagy via EGFR/MET signaling in lung adenocarcinoma.

High-throughput RNA-sequencing studies of tumor samples have identified a large number of long non-coding RNAs (lncRNAs) which are associated with various types of cancer. LncRNAs play key roles in regulating chromatin dynamics, gene expression, growth, differentiation and development. However, the role of in non-small cell lung cancer (NSCLC) tumorigenesis is not clear.

Interacting with YBX1 to Regulate Apoptosis and Autophagy via MET and Phosphor-AMPKa Signaling.

Long noncoding RNA (lncRNA) has been reported to be upregulated in lung cancer and related to poor patient survival. It can regulate cell proliferation and tumor growth in lung cancer as well as several other cancers. However, the underlying molecular mechanisms that are regulated by are unclear.

Influence of ligand substitution at the donor and acceptor center on MMCT in a cyanide-bridged mixed-valence system.

We detail the rational design of bimetallic cyanide-bridged complexes [TpmRu(L)(μ-CN)Ru(L)Cp*][PF] (Tpm = Tris(1-pyrazolyl)methane, L = 1,10-phenanthroline (phen), 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (dbpy), L = bis(diphenylphosphino)methane (dppm), bis(diphenylphosphino)ethane (dppe), Cp* = 1,2,3,4,5-pentamethylcyclopentadiene). The metal-to-metal charge transfer (MMCT) properties of these one-electron oxidized complexes were investigated, suggesting that the substitution of the ancillary ligand provides a strong impetus to systematically tune the MMCT properties. The investigation results indicate that all the mixed-valence complexes belong to Class II mixed-valence complexes, according to the Robin-Day classification.

Copper-catalyzed 1,4-alkylarylation of 1,3-enynes with masked alkyl electrophiles.

Classical 1,4-dicarbofunctionalization of 1,3-enynes employs organometallic reagents as nucleophiles to initiate the reaction. We report a copper-catalyzed 1,4-alkylarylation of 1,3-enynes with alkyl diacyl peroxides as masked alkyl electrophiles and aryl boronic acids as nucleophiles, selectively affording structurally diversified tetrasubstituted allenes under mild conditions. Mechanistic studies suggest that an allenyl radical might be involved.

Different Degrees of Electron Delocalization in Mixed Valence Ru-Ru-Ru Compounds by Cyanido-/Isocyanido-Bridge Isomerism.

The two stable pairs of trimetallic compounds trans-[Cp*(dppe)Ru(μ-NC)Ru(dmap) (μ-CN)Ru(dppe)Cp*][PF ] (1[PF ] , n=2, 3; Cp*=1,2,3,4,5-pentamethylcyclopentadiene; dppe=1,2-bis-(diphenylphosphino)ethane; dmap= 4-dimethylaminopyridine) and trans-[Cp*(dppe)Ru(μ-CN)Ru(dmap) (μ-NC)Ru(dppe)Cp*][PF ] (2[PF ] , n=2, 3), which demonstrate cyanide/isocyanide isomerism, have been synthesized and fully characterized. 1 [PF ] and 2 [PF ] are the one-electron oxidation products of 1 [PF ] and 2 [PF ] , respectively. The results suggest that 1[PF ] is a class III mixed valence compound, whereas 2[PF ] might be an unusually symmetrical class II-III mixed valence compound composed of the two asymmetrical delocalized Ru -NC-Ru mixed valence subunits.

Introduction of Red-Green-Blue Fluorescent Dyes into a Metal-Organic Framework for Tunable White Light Emission.

The unique features of the metal-organic frameworks (MOFs), including ultrahigh porosities and surface areas, tunable pores, endow the MOFs with special utilizations as host matrices. In this work, various neutral and ionic guest dye molecules, such as fluorescent brighteners, coumarin derivatives, 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM), and 4-(p-dimethylaminostyryl)-1-methylpyridinium (DSM), are encapsulated in a neutral MOF, yielding novel blue-, green-, and red-phosphors, respectively. Furthermore, this study introduces the red-, green-, and blue-emitting dyes into a MOF together for the first time, producing white-light materials with nearly ideal Commission International ed'Eclairage (CIE) coordinates, high color-rendering index values (up to 92%) and quantum yields (up to 26%), and moderate correlated color temperature values.

Homochiral Metal-Organic Frameworks with Tunable Nanoscale Channel Array and Their Enantioseparation Performance against Chiral Diols.

Enantioseparation is an integral process in the pharmaceutical industry, considering the ever-increasing demand for chiral medicine products. As a new material, porous metal-organic frameworks (MOFs) have shown their potential application in this field because their structures are easy to adjust and control. Though chiral recognition between racemic substrates and frameworks has made preliminary progress, discussions of their size-matching effects are rare.

Redox effects of low-spin Ru(ii/iii) on slow magnetic relaxation of Ru-Mn(iii) 1D cyanide-bridged complexes.

A new one-dimensional cyanide-bridged complex [Mn(salphen)Ru(DMAP)(CN)](PF) (1) and its oxidized derivative [Mn(salphen)Ru(DMAP)(CN)](PF) (2) have been synthesized and fully characterized. Magnetic measurements showed that 1 shows simple paramagnetism but 2 shows intrachain ferromagnetic interaction with slow magnetic relaxation.

Benzoquinone-bridged Co complexes with different magnetic anisotropy induced by solvent molecules.

The first example of discrete small molecular compounds with different magnetic anisotropy induced by solvent molecules, benzoquinone-bridged Co complexes, [(TPyA)Co(L)]·solvent (L = 2,5-dibromo-3,6-dihydroxy-1,4-benzoquinone, solvent = CHCN and HO), has been prepared and fully characterized.

An Unusually Delocalized Mixed-Valence State of a Cyanidometal-Bridged Compound Induced by Thermal Electron Transfer.

The heterometallic complexes trans-[Cp(dppe)FeNCRu(o-bpy)CNFe(dppe)Cp][PF ] (1[PF ] , n=2, 3, 4; o-bpy=1,2-bis(2,2'-bipyridyl-6-yl)ethane, dppe=1,2-bis(diphenylphosphino)ethane, Cp=1,3-cyclopentadiene) in three distinct states have been synthesized and fully characterized. 1 [PF ] and 1 [PF ] are the one- and two-electron oxidation products of 1 [PF ] , respectively. The investigated results suggest that 1[PF ] is a Class II mixed valence compound.

Effects of Ru(ii/iii) redox on the Co(ii) coordination number and magnetic properties of 1D cyanide-bridged Co-Ru compounds.

A new 1D cyanide-bridged Co-Ru compound, {[trans-Ru(dmap)(CN)Co(dipic)(MeOH)](PF)} (1a) (dmap = 4-dimethylaminopyridine, dipic = pyridine-2,6-dicarboxylate), and its reduced state, [trans-Ru(dmap)(CN)Co(dipic)] (1b) have been synthesized. Upon the Ru center reduction from iii to ii, the MeOH solvent molecule bound to Co(ii) in 1a is expelled. 1a displays ferrimagnetic properties but 1b is only a paramagnetic compound.

1D to 3D and Chiral to Noncentrosymmetric Metal-Organic Complexes Controlled by the Amount of DEF Solvent: Photoluminescent and NLO Properties.

A mixture of 2D and 1D metal-organic complexes, [ZnL(H2O)2·G1·DEF·2H2O]n (1a: G1 = naphthalene-2,7-disulfonate; DEF = N,N-diethylformamide) and [ZnL(H2O)3·G1·DEF·2H2O]n (2), has been prepared from a hydrogenated Schiff base L and Zn(II) in a DEF-contained solvent system under mild conditions. The yields of 1a and 2 are equivalent; however, they can be tuned by varying the amount of DEF solvent. Increasing the use of DEF tends to form pure 1a, while decreasing it generates 2.

Intercalation of Varied Sulfonates into a Layered MOC: Confinement-Caused Tunable Luminescence and Novel Properties.

The pores/channels of porous 3D metal-organic frameworks (MOFs) have been widely applied to incorporate gas, solvent, or organic molecules. On the contrary, the utilization of the interlamellar void of layered metal-organic complexes (MOCs) remains underappreciated, although it is more flexible and available to accommodate molecules with different sizes. In this work, diverse sulfonates have been intercalated purposely into an identical layered MOC, which constructed various novel intercalation compounds possessing fluorescent, white-light emitting, photochromic, homochiral, or nonlinear optical (NLO) properties.

A Luminescent Metal-Organic Framework Thermometer with Intrinsic Dual Emission from Organic Lumophores.

A new mixed-ligand metal-organic framework (MOF), ZnATZ-BTB, has been constructed as a luminescent ratiometric thermometer by making use of the intrinsic dual emission at cryogenic temperatures. Its twofold interpenetrated network promotes the Dexter energy transfer (DET) between the mixed organic lumophores. The temperature-dependent luminescent behavior arises from the thermal equilibrium between two separated excited states coupled by DET, which is confirmed by Boltzmann distribution fitting.

From pair quadruple- to single-stranded helices to lines in a mixed ligand system via adjusting the N-substituent of L-Glu.

Utilizing the mixed-ligand strategy, a novel fourfold-interpenetrated 3D homochiral metal-organic framework (1) with rare pair quadruple-stranded helices was assembled from bpee (1,2-bis(4-pyridyl)ethylene) and NCG (N-carbamyl-l-glutamate). Changing the carbamyl substituent of NCG with benzoyl group (NBzG: N-benzoyl-l-glutamate), a non-interpenetrated 3D homochiral coordination polymer (2) composed of alternate right-handed and left-handed single helix was obtained. When p-tolylsulfonyl substituent was used instead, an interesting homochiral linear structure (3) was formed from mixed-ligand bpee and NTsG (N-p-tolylsulfonyl-l-glutamate), with all individual NTsG being lined up orderly.

Influence of the central diamagnetic cyanidometal on the distant magnetic interaction in cyanide-bridged Fe(III)-M(II)-Fe(III) complexes.

To investigate how the central diamagnetic cyanidometal influences the distant magnetic interaction of cyanide-bridged Fe(III)-M(II)-Fe(III) complexes, cis-[Cp(dppe)Fe(II)(NC)M(II)(L)2(CN)Fe(II)(dppe) Cp][PF6]2 (M = Os, L = bpy 1; M = Os, L = phen 2; M = Fe, L = bpy 3; M = Fe, L = phen 4), and their one-electron oxidation products 5–7 and two-electron oxidation products 8–11 were synthesized and fully characterized. The cyclic voltammetry of complexes 1–4 suggests that both NC-Os(II)(L)2-CN and NC-Fe(II)(L)2-CN have electronic communication ability. The electronic absorption spectroscopy suggests the presence of the central M(II) to the terminal Fe(III) and the terminal Fe(II) to the terminal Fe(III) metal to metal charge transfers (MMCTs) in 5-7 and the central M(II) to the terminal Fe(III) MMCTs in 8-11.

Syntheses, structures, and properties of a series of novel high-nuclear 3d-4f clusters with mixed amino acids as ligands: {Ln6Cu24}(Ln = Gd, Tb, Pr and Sm).

The first examples of high-nuclear 3d-4f heterometallic clusters with mixed amino acid ligands are reported. Four 30-nuclear clusters {Ln6Cu24}(Ln = Gd, Tb, Pr and Sm) were obtained through the self-assembly of Ln(III), Cu(II) and mixed amino acid ligands of glycine (HGly) and β-alanine (HAla). The metal skeleton of clusters may be described as a huge {Ln6Cu12} octahedron connected with 12 additional Cu(II) ions.

Insight into luminescence enhancement of coordinated water-containing lanthanide metal-organic frameworks by guest molecules.

A series of isostructural lanthanide three-dimensional compounds [Ln(HL)(H2O)2]·guest (Ln = Tb or Eu, = 2-(N,N-bis(4-methylbenzoic acid)amino)benzoic-1,4-dioic acid, guest = NMP, DMA, DMF or H2O) were assembled and characterized. Their luminescence intensities and quantum yields increase in the order of the guest molecules: NMP > DMA > DMF > H2O (NMP = N-methyl-2-pyrrolidone, DMA = N,N-dimethylacetamide, DMF = N,N-dimethylformamide). The investigation reveals that the hydrogen-bond formed between the metal-organic frameworks should be responsible for the luminescence enhancement of the compounds.