Coinage metal(I) clusters supported by a 1,10-phenanthroline-phosphine: orange-to-NIR phosphorescence, metallophilic interactions and enhanced cytotoxicity.

A series of small coinage metal(I) clusters has been selectively synthesized using 2-(diphenylphosphino)-1,10-phenanthroline (L), a new promising dimetal-binding -ligand (L). Its reaction with CuI yields the complex [CuL(μ-I)][CuI], while the treatment of L with Au(tht)Cl/Ag or Au(tht)Cl/Cu systems leads to the assembly of [AuAgLCl], [AuCuLCl], [CuAuL] and [AgAuL] clusters. Theoretical analysis revealed pronounced intermetallic close shell interactions in these di- and trinuclear ensembles.

N^N^C-Cyclometalated rhodium(III) complexes with isomeric pyrimidine-based ligands: unveiling the impact of isomerism on structural motifs, luminescence and cytotoxicity.

The impact of isomerism of pyrimidine-based ligands and their rhodium(III) complexes with regard to their structures and properties was investigated. Two isomeric ligands, 4-(3,5-dimethyl-1-pyrazol-1-yl)-2,5-diphenylpyrimidine (HL2,5) and 4-(3,5-dimethyl-1-pyrazol-1-yl)-2,6-diphenylpyrimidine (HL2,6), were synthesized. The ligands differ by the degree of steric bulk: the molecular structure of HL2,5 is more distorted due to presence of pyrazolyl and phenyl groups in the neighbouring positions 4 and 5 of the pyrimidine ring.

Luminescent Supramolecular Ionic Frameworks based on Organic Fluorescent Polycations and Polyanionic Phosphorescent Metal Clusters.

Emissive ionic supramolecular frameworks are designed by associating tetraphenylethylene-based tetra-cationic units and di-anionic molybdenum or tetra-anionic rhenium octahedral clusters. Obtained structures were characterized by single-crystal X-ray diffraction. The emission properties of the hybrids were investigated as dry powders or in various solvents by one photon and two photon absorption leading to a O concentration dependent luminescence color for the Mo based hybrid.

Lanthanide complexes with a new luminescent iminophosphonamide ligand bearing phenylbenzothiazole substituents.

A new iminophosphonamine PhP(HNPbt)(NPbt) (1, HL) bearing chromophore 2-(phen-2'-yl)-1,3-benzothiazole (Pbt) substituents was synthesized and introduced into lanthanide complexes. It was found that salt metathesis reactions between KL (2) generated and LnCl lead to the formation of tris-iminophosphonamide complexes [LnL]L (Ln = Y (3), Sm (4), Gd (5), Dy (6)), regardless of the 2/LnCl ratio. Compounds 3-6 consist of a cationic fragment [LnL], where the lanthanide atom is surrounded by two rigidly κ-coordinated ligands, and an L anion residing in the outer coordination sphere.

Pd(II)- and Pt(II)-Assisted P-C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine.

There is unceasing interest toward transformations of phosphine derivatives, which are facilitated by transition metals. We report a facile Pd(II)- and Pt(II)-assisted P-C bond cleavage in a luminescent 2-phenylbenzothiazole-based α-methylaminophosphine (, ). Specifically, reactions between and [M(COD)Cl] (M = Pd, Pt; COD = cycloocta-1,5-diene) in different solvents (methylene chloride, acetonitrile, pyridine, toluene) resulted in the formation of PPh, captured either as a bridging ligand in binuclear complexes with a {M(PPh)} moiety or as an adduct to COD in [Pt(PPhCOD)Cl].

Exfoliation of 2D Metal-Organic Frameworks: toward Advanced Scalable Materials for Optical Sensing.

Two-dimensional metal-organic frameworks (MOFs) occupy a special place among the large family of functional 2D materials. Even at a monolayer level, 2D MOFs exhibit unique sensing, separation, catalytic, electronic, and conductive properties due to the combination of porosity and organo-inorganic nature. However, lab-to-fab transfer for 2D MOF layers faces the challenge of their scalability, limited by weak interactions between the organic and inorganic building blocks.

Synthesis, Structure, and Magnetic and Biological Properties of Copper(II) Complexes with 1,3,4-Thiadiazole Derivatives.

New coordination compounds of copper(II) with 2,5-bis(ethylthio)-1,3,4-thiadiazole (L) and 2,5-bis(pyridylmethylthio)-1,3,4-thiadiazole (L) with compositions Cu(L)Br, Cu(L)(CN), Cu(L)Cl, and Cu(L)Br were prepared. The complexes were identified and studied by CHN analysis, infrared (IR) spectroscopy, powder X-Ray diffraction (XRD), and static magnetic susceptibility. The crystal structures of Cu(II) complexes with L were determined.

Chromium-Lanthanide Complexes Containing the Cr═P═Cr Fragment: Synthesis, Characterization, and Computational Study.

Heterometallic complexes [Cp*Ln(μ-CO){Cr(μ-P)Cp(CO)}] [Ln = Yb (), Sm ()] were obtained in reactions of [Cp*Ln(thf)] (Ln = Sm, Yb) with [{CpCr(CO)}(μ,η-P)] (). An analogous yttrium compound [Cp*Y(μ-CO){Cr(μ-P)Cp(CO)}] () was synthesized using a three-component reaction between [Cp*Y(BPh)], , and KC. Compounds - were isolated as solvent-free crystalline phases; in the case of , the solvate was also obtained.

Luminescence of ESIPT-capable zinc(II) complexes with a 1-hydroxy-1-imidazole-based ligand: exploring the impact of substitution in the proton-donating moiety.

The rational design of ESIPT-capable metal complexes (ESIPT - Excited State Intramolecular Proton Transfer) requires two sites, namely, an ESIPT site and a metal binding site, to be spatially separated into the ligand core. Ligands featuring such sites are able to bind metal ions without being deprotonated upon their coordination. The use of ESIPT-capable ligands for the synthesis of metal complexes paves the way toward the exploration of ESIPT in the field of coordination chemistry.

Copper- and Silver-Containing Heterometallic Iodobismuthates: Features of Thermochromic Behavior.

Nine heterometallic iodobismuthates with the general formula Cat{[BiMI}] (M = Cu(I), Ag(I), Cat = organic cation) were synthesized. According to X-ray diffraction data, their crystal structures consisted of {BiI} units interconnected with Cu(I) or Ag(I) atoms through I-bridging ligands, forming one-dimensional polymers. The compounds are thermally stable up to 200 °C.

Improved Synthesis of (TBA)[WBr] Paving the Way to Further Study of Bromide Cluster Complexes.

Octahedral cluster complexes of molybdenum and tungsten, [MXY] (M = Mo, W; X, Y = Cl, Br, I), are promising active components in various fields, including biomedicine and solar energy. Cluster complexes draw considerable attention due to their X-ray opacity, red/near-IR luminescence, and ability to convert triplet molecular oxygen to active singlet oxygen under UV and visible irradiation. Among the octahedral cluster complexes of molybdenum and tungsten, compounds with a {WBr} core are the least studied.

Low-Coordinate Mixed Ligand NacNac Complexes of Rare Earth Metals.

We report the synthesis and characterization of two types of new mixed-ligand rare earth complexes: tetracoordinate (NacNac)Ln(BIAN) (Ln = Dy (), Er () and Y ()) and pentacoordinate (NacNac)Ln(AP)(THF) (Ln = Dy (), Er () and Y ()). The first three compounds were prepared by the reaction of [(BIAN)LnI] with potassium β-diketiminate. The salt metathesis of β-diketiminato-supported rare earth dichlorides (NacNac)LnCl(THF) with sodium o-amidophenolate results in compounds -.

Fluorescence vs. Phosphorescence: Which Scenario Is Preferable in Au(I) Complexes with Benzothiadiazoles?

The photoluminescence of Au(I) complexes is generally characterized by long radiative lifetimes owing to the large spin-orbital coupling constant of the Au(I) ion. Herein, we report three brightly emissive Au(I) coordination compounds, , and , that reveal unexpectedly short emission lifetimes of 10-20 ns. Polymorphs and exclusively exhibit fluorescence, which is quite rare for Au(I) compounds, while compound reveals fluorescence as the major radiative pathway, and a minor contribution of a microsecond-scale component.

Replenishment in the Family of Rhenium Chalcobromides; Synthesis and Structure of Molecular {ReS}Br(TeBr), Dimeric [{ReS}Br(TeBr)], and Polymeric {ReS}Br Compounds Based on the {ReS} Tetrahedral Cluster Core.

We have obtained three new rhenium(IV) chalcobromides belonging to the homologous series {ReS}Br(TeBr) ( = 0, 3, 4): a molecular complex {ReS}Br(TeBr) (), a dimeric complex [{ReS}(TeBr)Br(μ-Br)] (), and a two-dimensional (2D) polymeric compound {ReS}Br (). Compound is isotypic to the already known {ReTe}(TeBr)Br, while and exhibit a new type of binding of tetrahedral clusters via μ-Br bridges. Compounds were characterized by X-ray single-crystal diffraction, X-ray powder diffraction, and thermal and elemental analyses.

Octahedral Rhenium Cluster Complexes with 1,2-Bis(4-pyridyl)ethylene and 1,3-Bis(4-pyridyl)propane as Apical Ligands.

A series of eight new octahedral rhenium cluster complexes with the general formula -[{ReQ}LX] (Q = S or Se; L = 1,2-Bis(4-pyridyl)ethylene (bpe) or 1,3-Bis(4-pyridyl)propane (bpp); X = Cl or Br) was synthesized and investigated. While bpe is a ligand with a conjugated aromatic system, bpp represents a molecule of opposite type and has independent aromatic systems of the two pyridine rings. It was shown that this difference in the electronic structure of the ligands has a fundamental effect on the electronic structure, electrochemical and luminescent properties of the corresponding cluster complexes.

Coordination Polymers Based on Rhenium Octahedral Chalcocyanide Cluster Anions and Ag Cations with Bipyridine Analogs.

A series of six coordination polymers based on octahedral cluster anions [ReQ(CN)] (Q = S or Se) and Ag cations coordinated by bipyridine analogs were synthesized under solvothermal conditions. Their structures have been characterized by single crystal X-ray diffraction. Compounds and described by the general formula [{Ag(phen)}ReQ(CN)] (Q = Se (), S (); phen = 1,10-phenanthroline) exhibit layered structures assembled into a supramolecular network by CH…π contacts.

Selective Oxidation of Inner Pnictogenide Ligands in Mixed-Ligand Rhenium Cubane-Type Cluster Complexes.

Reactivity of new tetrahedral rhenium cluster complexes with pnictogenide inner ligands μ-As, μ-Sb, and μ-Bi has been investigated in reactions with aqueous HO. It has been found that the oxidation of clusters [{ReAsQ}(CN)] (Q = S or Se) led to the formation of stable clusters with μ-(AsO) ligands. Under the same conditions, the oxidation of [{ReAsS}(CN)] cluster led to substitution of μ-As ligands to μ-O.

Structural Diversity and Carbon Dioxide Sorption Selectivity of Zinc(II) Metal-Organic Frameworks Based on Bis(1,2,4-triazol-1-yl)methane and Terephthalic Acid.

A three-component reaction between the 1,4-benzenedicarboxylic (terephthalic) acid (Hbdc), bis(1,2,4-triazol-1-yl)methane (btrm) and zinc nitrate was studied, and three new coordination polymers were isolated by a careful selection of the reaction conditions. Coordination polymers {[Zn(DMF)(btrm)(bdc)]·nDMF} and {[Zn(btrm)(bdc)]·nDMF} containing trinuclear {Zn(bdc)} secondary building units are joined by btrm auxiliary linkers into three-dimensional metal-organic frameworks. The coordination polymer {[Zn(bdc)(btrm)]∙nDMF} consists of Zn cations joined by bdc and btrm linkers into a two-fold interpenetrated network.

Structural Diversity and Multielectron Reduction Reactivity of Samarium(II) Iodido-β-diketiminate Complexes Dependent on Tetrahydrofuran Content.

The molecular structures of complexes [Sm(Nacnac)I(thf)] (Nacnac = HC(C(Me)Ndipp), dipp = 2,6-diisopropylphenyl, thf = tetrahydrofuran) depending on the number of thf ligands are studied. The complete removal of thf from a known complex [Sm(Nacnac)I(thf)] leads to a tetranuclear product [Sm(Nacnac)I] (). The partial removal of thf results in mixtures of dinuclear [Sm(Nacnac)I(thf)] (), trinuclear [Sm(Nacnac)I(thf)] (), and tetranuclear [Sm(Nacnac)I(thf)] () complexes and , depending on the conditions.

Molecular Environment Effects That Modulate the Photophysical Properties of Novel 1,3-Phosphinoamines Based on 2,1,3-Benzothiadiazole.

We report synthesis, crystal structure, and photophysical properties of novel 1,3-phosphinoamines based on 4-amino-2,1,3-benzothiadiazole (NH-): PhPCH(Ph)NH- () and PhP(E)CH(Ph)NH-, (E = O ( and ·thf), S (), Se ()). Chalcogenides - exhibit bright emissions with a major band at 519-536 nm and a minor band at 840 nm. According to TD-DFT calculations, the first band is attributed to fluorescence, while the second band corresponds to phosphorescence.

Sterically Hindered Tellurium(IV) Catecholate as a Lewis Acid.

Sterically hindered tellurium catecholate Te(Cat) (Cat = 3,6-di--butyl-catecholate) was synthesized with the reaction of amorphous Te with 3,6-di--butyl--benzoquinone. Adducts of Te(Cat) with various O- and N-donors were isolated and characterized by means of single-crystal X-ray diffraction along with IR, UV-vis, and NMR (H, C, and Te) spectroscopies. In the crystal structure of the adduct with 2,2'-bipyridine (bipy), the unprecedented μ-κ,':κ,'-bridging coordination mode of bipy was observed.

Zn(II) and Co(II) 3D Coordination Polymers Based on 2-Iodoterephtalic Acid and 1,2-bis(4-pyridyl)ethane: Structures and Sorption Properties.

Metal-organic frameworks [M(2-I-bdc)bpe] (M = Zn(II) (), Co(II) (), 2-I-bdc = 2-iodoterephtalic acid, and bpe = 1,2-bis(4-pyridyl)ethane) were prepared and characterized by X-ray diffractometry. Both compounds retain their 3D structure after the removal of guest DMF molecules. Selectivity of sorption of different organic substrates from the gas phase was investigated for both complexes.

Structural Diversity of Silver Fluorinated β-Diketonates: Effect of the Terminal Substituent and Solvent.

In order to demonstrate the role of the fluorination and some solvents in the structural organization of the Ag(I) coordination polymers with β-diketonate ligands (RC(O)CHC(O)R) we synthesized a series of the compounds containing tfac- (R = CH, R = CF) and pfpac- (R = CH, R = CF) anions. Solvent-free [Ag(L)] (L = tfac , pfpac ) compounds and the corresponding acetonitrile and toluene adducts have been characterized by elemental analysis and/or NMR, IR and single-crystal XRD. This series includes five new coordination polymers.

Synthesis, Crystal Structure, and Luminescence of Cadmium(II) and Silver(I) Coordination Polymers Based on 1,3-Bis(1,2,4-triazol-1-yl)adamantane.

Coordination polymers with a new rigid ligand 1,3-bis(1,2,4-triazol-1-yl)adamantane (L) were prepared by its reaction with cadmium(II) or silver(I) nitrates. Crystal structure of the coordination polymers was determined using single-crystal X-ray diffraction analysis. Silver formed two-dimensional coordination polymer [Ag(L)NO], in which metal ions are linked by 1,3-bis(1,2,4-triazol-1-yl)adamantane ligands, coordinated by nitrogen atoms at positions 2 and 4 of 1,2,4-triazole rings.