Orientational Self-Sorting in Octahedral Palladium Cages: Scope and Limitations of the "cis Rule".

Octahedral coordination cages of the general formula [Pd6L12](BF4)12 were obtained by combining [Pd(CH3CN)4](BF4)2 with heteroditopic N-donor ligands. Four different ligands were employed. These ligands have 3-pyridyl donor groups at one end and 4-pyridyl, imidazolyl, or triazolyl donor groups at the other end. According to a geometric analysis, cages with a cis configuration at the six metal centers should be preferred ("cis rule"). This prediction was corroborated by spectroscopic data and crystallographic analyses. Limitations of the "cis rule" were also encountered, and possible explanations are discussed.

Ru(II)-Arene Complexes of Curcumin and Bisdesmethoxycurcumin Metabolites.

Curcuminoids and their complexes continue to attract attention in medicinal chemistry, but little attention has been given to their metabolic derivatives. Here, the first examples of (arene)Ru(II) complexes with curcuminoid metabolites, tetrahydrocurcumin (THcurcH), and tetrahydrobisdesmethoxycurcumin (THbdcurcH) were prepared and characterized. The neutral complexes [Ru(arene)(THcurc)Cl] and [Ru(arene)(THbdcurc)Cl] (arene = cymene, benzene, or hexamethylbenzene) were characterized by NMR spectroscopy and ESI mass spectrometry, and the crystal structures of the three complexes were determined by X-ray diffraction analysis. Compared to curcuminoids, these metabolites lose their conjugated double bond system responsible for their planarity, showing unique closed conformation structures. Both closed and open conformations have been analyzed and rationalized by using density functional theory (DFT). The cytotoxicity of the complexes was evaluated in vitro against human ovarian carcinoma cells (A2780 and A2780cisR), human breast adenocarcinoma cells (MCF-7 and MCF-7CR), as well as against non-tumorigenic human embryonic kidney cells (HEK293) and human breast (MCF-10A) cells and compared to the free ligands, cisplatin, and RAPTA-C. There is a correlation between cellular uptake and the cytotoxicity of the compounds, suggesting that cellular uptake and binding to nuclear DNA may be the major pathway for cytotoxicity. However, the levels of complex binding to DNA do not strictly correlate with the cytotoxic potency, indicating that other mechanisms are also involved. In addition, treatment of MCF-7 cells with [Ru(cym)(THcurc)Cl] showed a significant decrease in p62 protein levels, which is generally assumed as a noncisplatin-like mechanism of action involving autophagy. Hence, a cisplatin- and a noncisplatin-like concerted mechanism of action, involving both apoptosis and autophagy, is possible.

Metal-Mediated Synthesis of a Mixed Arduengo-Fischer Carbodicarbene Ligand.

Carbodicarbenes are strong C-donor ligands, which have found numerous applications in organometallic and main group element chemistry. Herein, we report a structurally distinct carbodicarbene ligand, which is formed by dinitrogenative coupling of a Fischer carbene complex with an N-heterocyclic diazoolefin. The resulting carbonyl complex serves as a stable source for the mixed Arduengo-Fischer carbodicarbene ligand. Facile ligand transfer reactions were demonstrated to occur with gold(I), copper(I), palladium(II), and rhodium(I) complexes.

Multimetallic Uranium Nitride Cubane Clusters from Dinitrogen Cleavage.

Dinitrogen cleavage provides an attractive but poorly studied route to the assembly of multimetallic nitride clusters. Here, we show that the monoelectron reduction of the dinitrogen complex [{U(OC6H2-But3-2,4,6)3}2(µ-η2:η2-N2)], 1, allows us to generate, for the first time, a uranium complex presenting a rare triply reduced N2 moiety ((µ-η2:η2-N2)•3-). Importantly, the bound dinitrogen can be further reduced, affording the U4N4 cubane cluster, 3, and the U6N6 edge-shared cubane cluster, 4, thus showing that (N2)•3- can be an intermediate in nitride formation. The tetranitride cluster showed high reactivity with electrophiles, yielding ammonia quantitatively upon acid addition and promoting CO cleavage to yield quantitative conversion of nitride into cyanide. These results show that dinitrogen reduction provides a versatile route for the assembly of large highly reactive nitride clusters, with U6N6 providing the first example of a molecular nitride of any metal formed from a complete cleavage of three N2 molecules.

Uranium(IV) and Thorium(IV) Coordination Polymers Based on Tritopic Carboxylic Acids.

Nine new coordination polymers based on U(IV) and Th(IV) were synthesized solvothermally utilizing four different trianionic carboxylates (H3BHTC = biphenyl-3,4',5-tricarboxylic acid, H3NTB = 4,4',4″-nitrilotribenzoic acid, H3BTB = 4,4',4″-benzene-1,3,5-triyl-tris(benzoic acid), H3BTE = 4,4',4″-(1,3,5-benzenetriyltri-2,1-ethynediyl)trisbenzoic acid). The influence of the ligand architecture, the pH, the stoichiometry, the nature of the metal, and the concentration on the structure and dimensionality of the final actinide assembly is discussed. The H3BHTC ligand allowed the synthesis of a cationic three-dimensional (3D) framework [U(BHTC)(DMF)3]I (1), which is the first example of a cationic U(IV) polymer. The H3NTB ligand yielded the 3D neutral polymer [U3(NTB)4] (2) or the two-dimensional (2D) cationic polymer [U(NTB)(NMP)3]I (3), depending on the solvent. When conditions leading to (2) were used with a Th(IV) precursor, the 2D neutral polymer [Th(NTB)(DMF)3Cl] (4) was obtained. The ligand H3BTB allowed the synthesis of two 3D cationic networks [U(BTB)(DMF)2]I (5) and [U(BTB)(DMF)3]I (7) or the neutral 3D analogue [U3(BTB)4] (6), depending on the precursor's oxidation state and the acidity of the reaction mixture. The ligand H3BTE allowed the synthesis of the anionic 3D [(CH3)2NH2][U2(BTE)3] (8) framework featuring large accessible pores, and under the same conditions, an isostructural Th(IV) was also obtained [(CH3)2NH2][Th2(BTE)3] (8-Th). All isolated coordination polymers were characterized by single-crystal X-ray diffraction (SCXRD). The Langmuir surface areas of the U(IV) polymers (2), (7), and (8) increased from 140 to 310 m2/g owing to the increasing size of the linker, with polymer (8) showing a value that is comparable to the highest surface area reported to date. The effect of the postsynthetic solvent substitution was also studied, revealing a crystal-to-crystal transformation of the cationic framework (7) to the neutral framework [U(BTB)(THF)I] (7c).

Synthetic Receptors with Micromolar Affinity for Chloride in Water.

A water-soluble coordination cage was obtained by reaction of Pd(NO3 )2 with a 1,3-di(pyridin-3-yl)benzene ligand featuring a short PEG chain. The cavity of the metal-organic cage contains one nitrate anion, which is readily replaced by chloride. The apparent association constant for chloride binding in buffered aqueous solution is Ka =1.8(±0.1)×105  M-1 . This value is significantly higher than what has been reported for other macrocyclic chloride receptors. The heavier halides Br- and I- compete with binding or self-assembly, but the receptor displays very good selectivity over common anions such as phosphate, acetate, carbonate, and sulfate. A further increase of the chloride binding affinity by a factor of 3 was achieved using a fluorinated dipyridyl ligand.

Synthesis and Reactivity of an Anionic Diazoolefin.

Bent (hetero)allenes such as carbodicarbenes and carbodiphosphoranes can act as neutral C-donor ligands, and diverse applications in coordination chemistry have been reported. N-Heterocyclic diazoolefins are heterocumulenes, which can function in a similar fashion as L-type ligands. Herein, we describe the synthesis and the reactivity of an anionic diazoolefin. This compound displays distinct reactivity compared to neutral diazoolefins, as evidenced by the preparation of diazo compounds via protonation, alkylation, or silylation. The anionic diazoolefin can be employed as an ambidentate, X-type ligand in salt metathesis reactions with metal halide complexes. Extrusion of dinitrogen was observed in a reaction with PCl(NiPr2 )2 , resulting in a stable phosphinocarbene.

Copper Complexes with Diazoolefin Ligands and their Photochemical Conversion into Alkenylidene Complexes.

Homometallic copper complexes with alkenylidene ligands are discussed as intermediates in catalysis but the isolation of such complexes has remained elusive. Herein, we report the structural characterization of copper complexes with bridging and terminal alkenylidene ligands. The compounds were obtained by irradiation of CuI complexes with N-heterocyclic diazoolefin ligands. The complex with a terminal alkenylidene ligand required isolation in a crystalline matrix, and its structural characterization was enabled by in crystallo photolysis at low temperature.

Head-to-Tail Dimerization of N-Heterocyclic Diazoolefins.

The head-to-tail dimerization of N-heterocyclic diazoolefins is described. The products of these formal (3+3) cycloaddition reactions are strongly reducing quinoidal tetrazines. Oxidation of the tetrazines occurs in a stepwise fashion, and we were able to isolate a stable radical cation and diamagnetic dications. The latter are also accessible by oxidative dimerization of diazoolefins.

A Mesoionic Diselenolene Anion and the Corresponding Radical Dianion.

Dichalcogenolenes are archetypal redox non-innocent ligands with numerous applications. Herein, a diselenolene ligand with fundamentally different electronic properties is described. A mesoionic diselenolene was prepared by selenation of a C2-protected imidazolium salt. This ligand is diamagnetic, which is in contrast to the paramagnetic nature of standard dichalcogenolene monoanions. The new ligand is also redox-active, as demonstrated by isolation of a stable diselenolene radical dianion. The unique electronic properties of the new ligand give rise to unusual coordination chemistry. Thus, preparation of a hexacoordinate aluminum tris(diselenolene) complex and a Lewis acidic aluminate complex with two ligand-centered unpaired electrons was achieved.

Synthesis and Reactivity of a Terminal 1-Alkynyl Triazene.

1-Alkynyl triazenes are versatile reagents in synthetic organic chemistry, but the structural diversity of this compound class has so far been limited. Herein, we describe the synthesis of a terminal 1-alkynyl triazene. Subsequent functionalization allows the preparation of 1-alkynyl triazenes with a range of functional groups including esters, alcohols, cyanides, phosphonates, and amides. Furthermore, the terminal 1-alkynyl triazene can be used for the synthesis of di- and triynes and for the preparation of (hetero)aromatic triazenes in metal-catalyzed cyclization reactions.

Structure and Reactivity of Polynuclear Divalent Lanthanide Disiloxanediolate Complexes.

Trinuclear molecular complexes of europium (II) and ytterbium(II) [Ln3{(Ph2SiO)2O}3(THF)6], 1-Ln3L3 (Ln = Eu and Yb), supported by the dianionic tetraphenyl disiloxanediolate ligand, were synthesized via protonolysis of the [Ln{N(SiMe3)2}2(THF)2] complexes. In contrast, the reaction of [Sm{N(SiMe3)2}2(THF)2] with the (Ph2SiOH)2O ligand led to the isolation of the mixed-valent Sm(II)/Sm(III) complex [Sm3{(Ph2SiO)2O}3{N(SiMe3)2}(THF)4], 2-Sm3L3, which was crystallographically characterized. The Eu(II) complex 1-Eu3L3 displays weak ferromagnetic coupling between the Eu(II) metal centers (J = 0.1035 cm-1). The addition of 3 equiv of (Ph2SiOK)2O to 1-Eu3L3 resulted in the formation of the polynuclear Eu(II) dimer of dimers [K4Eu2{(Ph2SiO)2O}4(Et2O)2]2, 3-Eu2L4. Complexes 1-Ln3L3 (Ln = Eu and Yb) are stable in solution at room temperature, while 3-Eu2L4 shows higher reactivity and rapidly decomposes to give the mixed-valent Eu(II)/Eu(III) species [K3Eu2{(Ph2SiO)2O}4], 4-Eu2L4. Complex 1-Yb3L3 affects the slow reductive disproportionation of carbon dioxide, but 1-Eu3L3 does not display any reactivity toward CO2. However, the presence of one additional (Ph2SiO-)2O per Eu(II) metal center in 3-Eu2L4 increases dramatically the reductive ability of the Eu(II) metal centers, affording the first example of carbon dioxide activation by an isolated divalent europium complex. The reduction of CO2 by 3-Eu2L4 is immediate, and carbonate is formed selectively after the addition of a stoichiometric amount of CO2.

The Chemistry of the Passivation Mechanism of Perovskite Films with Ionic Liquids.

Passivation of perovskite films by ionic liquids (ILs) improves the performance (efficiency and stability) of perovskite solar cells (PSCs). However, the role of ILs in the passivation of perovskite films is not fully understood. Here, we report the reactions of commonly used ILs with the components of perovskites. The reaction of ILs with perovskite precursors (PbI2 and methylammonium iodide or formamidinium iodide) in a 1:1:1 molar ratio affords one-dimensional (1D) salts composed of the IL cation interspersed along infinite 1D polymeric [PbI3]-n chains. If the IL is applied in excess, the resulting crystal is composed of six cations surrounding a discrete [Pb3I12]6- cluster. All the isolated salts were unambiguously characterized by single-crystal X-ray diffraction analysis, which also reveals extensive hydrogen-bonding interactions.

LiBF4 -Induced Rearrangement and Desymmetrization of a Palladium-Ligand Assembly.

Thirteen palladium-ligand assemblies with different structures and topologies were investigated for the ability to bind lithium ions. In one case, the addition of LiBF4 resulted in a profound structural rearrangement, converting a dincluclear [Pd2 L4 ]4+ complex into a low-symmetry [Pd4 L8 ]8+ assembly with two binding pockets for solvated LiBF4 ion pairs. The rearrangement could only be induced by Li+ , indicating highly specific host-guest interactions. A structural analysis of the [Pd4 L8 ]8+ receptor revealed a compact structure with multiple intramolecular interactions, reminiscent of what is seen for natural and synthetic foldamers.

Fluorinated Tetraarylethenes: Universal Tags for the Synthesis of Solid State Luminogens.

The aggregation-induced emission properties of tetraarylethenes (TAEs) have led to numerous applications in chemistry, biology, and materials science. Herein, we describe two fluorinated tetraarylethenes, which can be employed as universal tags for the synthesis of solid state luminogens. The tags are accessible in one or two steps from commercially available starting materials. Facile coupling reactions with ubiquitous substrates such as thiols, alcohols, amines, phosphines, aldehydes, and enamines allow preparing a wide range of TAE conjugates, including tagged amino acids, peptides, carbohydrates, steroids, and commercial polymers.

Stepwise Reduction of Dinitrogen by a Uranium-Potassium Complex Yielding a U(VI)/U(IV) Tetranitride Cluster.

Multimetallic cooperativity is believed to play a key role in the cleavage of dinitrogen to nitrides (N3-), but the mechanism remains ambiguous due to the lack of isolated intermediates. Herein, we report the reduction of the complex [K2{[UV(OSi(OtBu)3)3]2(µ-O)(µ-η2:η2-N2)}], B, with KC8, yielding the tetranuclear tetranitride cluster [K6{(OSi(OtBu)3)2UIV}3{(OSi(OtBu)3)2UVI}(µ4-N)3(µ3-N)(µ3-O)2], 1, a novel example of N2 cleavage to nitride by a diuranium complex. The structure of complex 1 is remarkable, as it contains a unique uranium center bound by four nitrides and provides the second example of a trans-N═UVI═N core analogue of UO22+. Experimental and computational studies indicate that the formation of the U(IV)/U(VI) tetrauranium cluster occurs via successive one-electron transfers from potassium to the bound N24- ligand in complex B, resulting in N2 cleavage and the formation of the putative diuranium(V) bis-nitride [K4{[UV(OSi(OtBu)3)3]2(µ-O)(µ-N)2}], X. Additionally, cooperative potassium binding to the U-bound N24- ligand facilitates dinitrogen cleavage during electron transfer. The nucleophilic nitrides in both complexes are easily functionalized by protons to yield ammonia in 93-97% yield and with excess 13CO to yield K13CN and KN13CO. The structures of two tetranuclear U(IV)/U(V) bis- and mononitride clusters isolated from the reaction with CO demonstrate that the nitride moieties are replaced by oxides without disrupting the tetranuclear structure, but ultimately leading to valence redistribution.

Identification of a Heteroleptic Pd6L6L'6 Coordination Cage by Screening of a Virtual Combinatorial Library.

The design of structurally defined heteroleptic coordination cages is a challenging task, and only few examples are known to date. Here we describe a selection approach that allowed the identification of a novel hexanuclear Pd cage containing two types of dipyridyl ligands. A virtual combinatorial library of [PdnL2n](BF4)2n complexes was prepared by mixing six different dipyridyl ligands with substoichiometric amounts of [Pd(CH3CN)4](BF4)2. Analysis of the equilibrated reaction mixture revealed the preferential formation of a heteroleptic [Pd6L6L'6](BF4)12 assembly. The complex was prepared on a preparative scale by a targeted synthesis, and its structure was elucidated by single-crystal X-ray diffraction. It features an unprecedented trigonal-antiprismatic cage structure with two triangular Pd3L3 macrocycles bridged by six L' ligands. A related but significantly larger [Pd6L6L'6](BF4)12 cage was obtained by using metalloligands instead of organic dipyridyl ligands.

Tuning the Size and Geometry of Heteroleptic Coordination Cages by Varying the Ligand Bent Angle.

Spherical assemblies of the type [Pdn L2n ]2n+ can be obtained from PdII salts and curved N-donor ligands, L. It is well established that the bent angle, α, of the ligand is a decisive factor in the self-assembly process, with larger angles leading to complexes with a higher nuclearity, n. Herein, we report heteroleptic coordination cages of the type [Pdn Ln L'n ]2n+ , for which a similar correlation between the ligand bent angle and the nuclearity is observed. Tetranuclear cages were obtained by combining [Pd(CH3 CN)4 ](BF4 )2 with 1,3-di(pyridin-3-yl)benzene and ligands featuring a bent angle of α=120°. The use of a dipyridyl ligand with α=149° led to the formation of a hexanuclear complex with a trigonal prismatic geometry; for linear ligands, octanuclear assemblies of the type [Pd8 L8 L'8 ]16+ were obtained. The predictable formation of heteroleptic PdII cages from 1,3-di(pyridin-3-yl)benzene and different dipyridyl ligands is evidence that there are entire classes of heteroleptic cage structures that are privileged from a thermodynamic point of view.

Structure-Property Relationships in Bithiophenes with Hydrogen-Bonded Substituents.

The use of crystal engineering to control the supramolecular arrangement of π-conjugated molecules in the solid-state is of considerable interest for the development of novel organic electronic materials. In this study, we investigated the effect of combining of two types of supramolecular interaction with different geometric requirements, amide hydrogen bonding and π-interactions, on the π-overlap between calamitic π-conjugated cores. To this end, we prepared two series of bithiophene diesters and diamides with methylene, ethylene, or propylene spacers between the bithiophene core and the functional groups in their terminal substituents. The hydrogen-bonded bithiophene diamides showed significantly denser packing of the bithiophene cores than the diesters and other known α,ω-disubstituted bithiophenes. The bithiophene packing density reach a maximum in the bithiophene diamide with an ethylene spacer, which had the smallest longitudinal bithiophene displacement and infinite 1D arrays of electronically conjugated, parallel, and almost linear N-H⋅⋅⋅O=C hydrogen bonds. The synergistic hydrogen bonding and π-interactions were attributed to the favorable conformation mechanics of the ethylene spacer and resulted in H-type spectroscopic aggregates in solid-state absorption spectroscopy. These results demonstrate that the optoelectronic properties of π-conjugated materials in the solid-state may be tailored systematically by side-chain engineering, and hence that this approach has significant potential for the design of organic and polymer semiconductors.

Tuning the π-Accepting Properties of Mesoionic Carbenes: A Combined Computational and Experimental Study.

Mesoionic imidazolylidenes are recognized as excellent electron-donating ligands in organometallic and main group chemistry. However, these carbene ligands typically show poor π-accepting properties. A computational analysis of 71 mesoionic imidazolylidenes that bear different aryl or heteroaryl substituents in C2 position was performed. The study has revealed that a diphenyltriazinyl (Dpt) substituent renders the corresponding carbene particularly π-acidic. The computational results could be corroborated experimentally. A mesoionic imidazolylidene with a Dpt substituent was found to be a better σ-donor and a better π-acceptor compared to an Arduengo-type N-heterocyclic carbene. To demonstrate the utility of the new carbene, the ligand was used to stabilize a low-valent paramagnetic tin compound.