Multi-functional architectures supported on organostannoxane scaffolds

Organostannoxane cages and aggregates of well-defined composition and structure can be prepared by the reactions of organotin oxides or organotin oxide-hydroxides with protic acids. The utility of this strategy for the preparation of dendrimer-like molecules containing a stannoxane core and a functional periphery is described

Stannoxanes and phosphonates: new approaches in organometallic and transition metal assemblies

Phosphonate ligands, [RPO3]2-, are extremely versatile in the assembly of multi-tin and multi-copper architectures. We have used organostannoxane cores for supporting multi-ferrocene and multi-porphyrin peripheries. The copper-metalated multi-porphyrin compound is an excellent reagent for facile cleavage of DNA, even in the absence of a co-oxidant. Reaction oft-BuPO3H2 with Cu(C104)2. 6H2O in the presence of 2-pyridylpyrazole (2-Pypz) leads to the synthesis of a decanuclear copper (II) assembly

Decanuclear Ln10 wheels and vertex-shared spirocyclic Ln5 cores: synthesis, structure, SMM behavior, and MCE properties

et al.The reaction of a Schiff base ligand (LH3) with lanthanide salts, pivalic acid and triethylamine in 1:1:1:3 and 4:5:8:20 stoichiometric ratios results in the formation of decanuclear Ln10 (Ln=Dy(1), Tb(2), and Gd (3)) and pentanuclear Ln5 complexes (Ln=Gd (4), Tb (5), and Dy (6)), respectively. The formation of Ln10 and Ln5 complexes are fully governed by the stoichiometry of the reagents used. Detailed magnetic studies on these complexes (1–6) have been carried out. Complex 1 shows a SMM behavior with an effective energy barrier for the reversal of the magnetization (Ueff)=16.12(8) K and relaxation time (τo)=3.3×10−5 s under 4000 Oe direct current (dc) field. Complex 6 shows the frequency dependent maxima in the out-of-phase signal under zero dc field, without achieving maxima above 2 K. Complexes 3 and 4 show a large magnetocaloric effect with the following characteristic values: −ΔSm=26.6 J kg−1 K−1 at T=2.2 K for 3 and −ΔSm=27.1 J kg−1 K−1 at T=2.4 K for 4, both for an applied field change of 7 T.We are thankful to the Department of Science and Technology, New Delhi, for financial support. S.D., A.D., S.K., and S.B. thank CSIR, India for Senior Research Fellowship. V.C. is thankful to the Department of Science and Technology for a J.C. Bose National Fellowship. EC is thankful for financial support to Ministerio de Economía y Competitividad (MINECO) for Projects CTQ-2011-24478, CTQ2014-56312-P, the Junta de Andalucía (FQM-195 and the Project of excellence P11-FQM-7756), the University of Granada financial support. M.E. acknowledges financial support from MINECO through grant MAT2012-38318-C03-01. ST thanks the Junta de Andalucía for a postdoctoral contract.Peer Reviewe

Heterometallic Octanuclear Ni(4)(II)Ln(4)(III) (Ln = Y, Gd, Tb, Dy, Ho, Er) Complexes Containing Ni(2)(II)Ln(2)(III)O(4) Distorted Cubane Motifs: Synthesis, Structure, and Magnetic Properties

The reaction of 2-methoxy-6-[{2-(2-hydroxyethylamino)ethylimino}methyl] phenol (LH3) with lanthanide metal salts followed by the addition of nickel acetate allowed isolation of a family of octanuclear complexes, [Ni4Ln4(μ2-OH)2(μ3- OH)4(μ-OOCCH3)8(LH2)4]·(OH)2·xH2O. Single crystal X-ray diffraction studies of these complexes reveal that their central metallic core consists of two tetranuclear [Ni2Ln2O4] cubane subunits fused together by acetate and hydroxide bridges. The magnetic study of these complexes reveals a ferromagnetic interaction between the LnIII and the NiII center. The magnitude of exchange coupling between the NiII and LnIII center, parametrized from the magnetic data of the Gd analogue, gives J = +0.86 cm−1. The magneto caloric effect, studied for the NiII 4GdIII 4 complex, shows a maximum of magnetic entropy change, −ΔSm = 22.58 J kg−1 K−1 at 3 K for an applied external field of 5 T.Ministerio de Economía y Competitividad (MINECO) and EU Feder Funds (Project CTQ2014-56312-P), the Junta de Andalucía (FQM-195 and the Project of Excellence P11-FQM- 7756), and the University of Granada for financial support

NHC-Coordinated Diphosphene-Stabilized Gold(I) Hydride and Its Reversible Conversion to Gold(I) Formate with CO2

An NHC-coordinated diphosphene is employed as ligand for the synthesis of a hydrocarbon-soluble monomeric AuI hydride, which readily adds CO2 at room temperature yielding the corresponding AuI formate. The reversible reaction can be expedited by the addition of NHC, which induces β-hydride shift and the removal of CO2 from equilibrium through the formation of an NHC-CO2 adduct. The AuI formate is alternatively formed by dehydrogenative coupling of the AuI hydride with formic acid (HCO2 H), thus in total establishing a reaction sequence for the AuI hydride mediated dehydrogenation of HCO2 H as chemical hydrogen storage material

Octanuclear heterobimetallic {Ni4Ln4} assemblies possessing Ln4 square grid [2×2] motifs : synthesis, structure and magnetism

Octanuclear heterobimetallic complexes, [Ln4Ni4(H3L)4(µ3-OH)4(µ2-OH)4]4Cl·xH2O·yCHCl3 (Dy3+ , x = 30.6, y = 2 (1); Tb3+ , x = 28, y = 0 (2) ; Gd3+ , x = 25.3, y = 0 (3); Ho3+ , x = 30.6, y = 3 (4)) (H5L = N1, N3-bis(6-formyl-2-(hydroxymethyl) -4-methylphenol) diethylenetriamine) are reported. These are assembled by the cumulative coordination action of four doubly deprotonated compartmental ligands, [H3L] 2- , along with eight exogenous –OH ligands. Within the core of these complexes, four Ln3+ are distributed to the four corners of a perfect square grid while four Ni2+ are projected away from the plane of the Ln4 unit. Each of the four Ni2+ possesses distorted octahedral geometry while all the Ln3+ are crystallographically equivalent and are present in an elongated square antiprism geometry. The magnetic properties of compound 3 are dominated by an easy-plane single-ion anisotropy of the Ni2+ ions [DNi = 6.7(7) K] and dipolar interactions between Gd3+ centers. Detailed ac magnetometry reveals the presence of distinct temperature-dependent out-of-phase signals for compounds 1 and 2, indicative of slow magnetic relaxation. Magnetochemical analysis of complex 1 implies the 3d and the 4f metal ions are engaged in ferromagnetic interactions with SMM behavior, while dc magnetometry of compound 2 is suggestive of an antiferromagnetic Ni-Tb spin-exchange with slow magnetic relaxation due to a field-induced level crossing. Compound 4 exhibits an easy-plane single-ion anisotropy for the Ho3+ ions and weak interactions between spin centers

Whose Side Are You On?

The cyclophosphazene hydrazides N3P3(N(Me)NH2)6 (1), spiro-N3P3(C12H8O2)(N(Me)NH2)4 (2), and dispiro-N3P3(C12H8O2)2(N(Me)NH2)2 (3) have been readily elaborated by a click synthesis involving condensation with pentafluorobenzaldehyde to afford the fluorine-rich cyclophosphazene hydrazones N3P3(N(Me)N=CHC6F5)6 (4), spiro-N3P3(C12H8O2)(N(Me)N=CHC6F5)4 (5), and dispiro-N3P3(C12H8O2)2(N(Me)N=CHC6F5)2 (6) in excellent yields. The molecular and crystal structures of 4-6 are reported. The crystal structures of 4-6 reveal a rich interplay of various intermolecular secondary interactions generating novel supramolecular architectures. The dependence of the molecular symmetry on the eventual supramolecular structures is also revealed. The crystal structure of 6 shows the selective entrapment of guest dioxane molecules

CAAC‐Based Thiele and Schlenk Hydrocarbons

Diradicals have been of tremendous interest for over a century ever since the first reports of p ‐ and m ‐phenylene‐bridged diphenylmethylradicals in 1904 by Thiele and 1915 by Schlenk. Reported here are the first examples of cyclic(alkyl)(amino)carbene (CAAC) analogues of Thiele's hydrocarbon, a Kekulé diradical, and Schlenk's hydrocarbon, a non‐Kekulé diradical, without using CAAC as a precursor. The CAAC analogue of Thiele's hydrocarbon has a singlet ground state, whereas the CAAC analogue of Schlenk's hydrocarbon contains two unpaired electrons. The latter forms a dimer, by an intermolecular double head‐to‐tail dimerization. This straightforward synthetic methodology is modular and can be extended for the generation of redox‐active organic compounds

Non‐Identical Stepwise Reversible Double‐Redox Coupled Bond Activation Reactions

This work presents a stepwise reversible two‐electron transfer induced hydrogen shift leading to the conversion of a bis‐pyrrolinium cation to an E ‐diaminoalkene and vice versa. Remarkably, the forward and the reverse reaction, which are both reversible, follow two completely different reaction pathways. Establishing such unprecedented property in this type of processes was possible by developing a novel synthetic route towards the starting dication. All intermediates involved in both the forward and the backward reactions were comprehensively characterized by a combination of spectroscopic, crystallographic, electrochemical, spectroelectrochemical, and theoretical methods. The presented synthetic route opens up new possibilities for the generation of multi‐pyrrolinium cation scaffold‐based organic redox systems, which constitute decidedly sought‐after molecules in contemporary chemistry

Twisted Push-Pull Alkenes Bearing Geminal Cyclicdiamino and Difluoroaryl Substituents

The systematic combination of N-heterocyclic olefins (NHOs) with fluoroarenes resulted in twisted push-pull alkenes. These alkenes carry electron-donating cyclicdiamino substituents and two electron-withdrawing fluoroaryl substituents in the geminal positions. The synthetic method can be extended to a variety of substituted push-pull alkenes by varying the NHO as well as the fluoroarenes. Solid-state molecular structures of these molecules reveal a notable elongation of the central C-C bond and a twisted geometry in the alkene motif. Absorption properties were investigated with UV-vis spectroscopy. The redox properties of the twisted push-pull alkenes were probed with electrochemistry as well as UV-vis/NIR and EPR spectroelectrochemistry, while the electronic structures were computationally evaluated and validated.Fil: Kundu, Abhinanda. International Centre Of Theoretical Science. Tata Institute Of Fundamental Research; EspañaFil: Chandra, Shubhadeep. Universitat Stuttgart; AlemaniaFil: Mandal, Debdeep. International Centre Of Theoretical Science. Tata Institute Of Fundamental Research; EspañaFil: Neuman, Nicolás Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Mahata, Alok. International Centre Of Theoretical Science. Tata Institute Of Fundamental Research; EspañaFil: Anga, Srinivas. International Centre Of Theoretical Science. Tata Institute Of Fundamental Research; EspañaFil: Rawat, Hemant. International Centre Of Theoretical Science. Tata Institute Of Fundamental Research; EspañaFil: Pal, Sudip. International Centre Of Theoretical Science. Tata Institute Of Fundamental Research; EspañaFil: Schulzke, Carola. ERNST MORITZ ARNDT UNIVERSITÄT GREIFSWALD (UG);Fil: Sarkar, Biprajit. Universität Stuttgart; AlemaniaFil: Chandrasekhar, Vadapalli. Indian Institute Of Technology Kanpur; IndiaFil: Jana, Anukul. Tata Institute Of Fundamental Research, Hyderabad; Indi