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showing 10 items of 55700 documents
Reappraising Schmidpeter's bis(iminophosphoranyl)phosphides: coordination to transition metals and bonding analysis
2020
The synthesis and characterization of a range of bis(iminophosphoranyl)phosphide (BIPP) group 4 and coinage metals complexes is reported. BIPP ligands bind group 4 metals in a pseudo fac-fashion, and the central phosphorus atom enables the formation of d0–d10 heterobimetallic complexes. Various DFT computational tools (including AIM, ELF and NCI) show that the phosphorus–metal interaction is either electrostatic (Ti) or dative (Au, Cu). A bridged homobimetallic Cu–Cu complex was also prepared and its spectroscopic properties were investigated. The theoretical analysis of the P–P bond in BIPP complexes reveals that (i) BIPP are closely related to ambiphilic triphosphenium (TP) cations; (ii) …
Crystallographic snapshots of host–guest interactions in drugs@metal–organic frameworks: towards mimicking molecular recognition processes
2018
We report a novel metal–organic framework (MOF) featuring functional pores decorated with hydroxyl groups derived from the natural amino acid L-serine, which is able to establish specific interactions of different natures, strengths and directionalities with organic molecules of technological interest, i.e. ascorbic acid, pyridoxine, bupropion and 17-β-estradiol, based on their different sizes and chemical natures. The ability of 1 to distinctly organize guest molecules within its channels, through the concomitant effect of different directing supramolecular host–guest interactions, enables gaining unique insights, by means of single-crystal X-ray crystallography, into the host–guest intera…
Role of the Open-Shell Character on the Pressure-Induced Conductivity of an Organic Donor-Acceptor Radical Dyad
2018
Single‐component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF‐Ph‐PTM derivative (1) are reported and implications of its crystal…
Single Enantiomer’s Urge to Crystallize in Centrosymmetric Space Groups: Solid Solutions of Phenylpiracetam
2017
A detailed thermochemical and structural study of the phenylpiracetam enantiomer system was performed by characterizing the solid solutions, rationalizing the structural driving force for their formation, as well as identifying a common structural origin responsible for the formation of solid solutions of enantiomers. Enantiomerically pure phenylpiracetam forms two enantiotropically related polymorphs (enant–A and enant–B). The transition point (70(7) °C) was determined based on isobaric heat capacity measurements. Structural studies revealed that enant–A and enant–B crystallize in space groups P1 (Z′ = 4) and P212121 (Z′ = 2), respectively. However, pseudoinversion centers were present res…
Effect of Guest Molecules on Spin Transition Temperature in Loaded Hofmann‐Like Clathrates with Improved Porosity
2020
The synthesis, crystal structure, magnetic and calorimetric studies of a new clathrate compound of the Hofmann-type spin crossover (SCO) metal-organic framework (MOF) {Fe(bpb)[MII(CN)4]}·xGuest (bpb = bis(4-pyridyl)butadiyne, and MII = Ni, Pt) with characteristic fsc topology is reported. The framework {Fe(bpb)[MII(CN)4]} can host up to 1.5 guest molecules of (trifluoromethyl)benzene and display complete one-step cooperative SCO behavior. Our systematic study on {Fe(bpb)[Pt(CN)4]}·xGuest shows a general reciprocal correlation between the SCO temperature with the volume of the guest molecules.
Supramolecular open-framework architectures based on dicarboxylate H-bond acceptors and polytopic cations with three/four N–H+donor units
2015
International audience; Supramolecular assemblages based on anionic H-acceptors and cationic H-donors have been envisioned to elaborate open frameworks maintained by ionic H-bonds. Combinations of di-anionic chloranilate (CA2-), oxalate (Ox2-), or terephthalate (BDC2-) and trisimidazolium or tetrapyridinium derivatives (three and four N-H+ donors, respectively) yielded five architectures of formulae [(H3TrIB)(CA)1.5[middle dot]2DMF[middle dot]2.5H2O] (1), [(H4Tetrapy)(CA)2[middle dot]3DMF] (2), [(H3TrIB)(HOx)(Ox)[middle dot]5H2O] (3), [(H4Tetrapy)(Ox)2[middle dot]5H2O] (4), and [(H4Tetrapy)(BDC)2(H2O)[middle dot]1DMF[middle dot]3H2O] (5) (with TrIB = 1,3,5-trisimidazolylbenzene and Tetrapy …
Diferratricarbaboranes of thesubcloso-[(η5-C5H5)2Fe2C3B8H11] Type, the First Representatives of the 13-Vertex Dimetallatricarbaborane Series
2003
Treatment of the [2-Cp-9-tBuNH-closo-2,1,7,9-FeC 3 B 8 H 1 0 ] (1) ferratricarbollide (Cp = η 5 -C 5 H 5 -) with Na + C 1 0 H 8 - in 1,2-dimethoxyethane (DME) at room temperature produced an air-sensitive transient anion with a tentatively identified nido-[tBUNH-CpFeC 3 B 8 H 1 0 ] 2 - constitution. In-situ reaction of this low-stability ion with [CpFe(CO) 2 I] or [CpFe(CO) 2 ] 2 generated three violet diferratricarbaboranes identified as paramagnetic subcloso complexes [4,5-Cp 2 - -4,5,1,6,7-Fe 2 C 3 B 8 H 1 1 ] (2; yield 2%), [4,5-Cp 2 - -4,5,1,7,12-Fe 2 C 3 B 8 H 1 1 ] (3; yield 2%), and [7-tBuNH-4,5-Cp 2 - -4,5,1,7,12-Fe 2 C 3 B 8 H 1 0 ] (4; yield 14%). These first representatives of t…
Chiral and Racemic Spin Crossover Polymorphs in a Family of Mononuclear Iron(II) Compounds
2017
[EN] Understanding the origin of cooperativity and the equilibrium temperature of transition (T1/2) displayed by the spin-crossover (SCO) compounds as well as controlling these parameters are of paramount importance for future applications. For this task, the occurrence of polymorphism, presented by a number of SCO complexes, may provide deep insight into the influence of the supramolecular organization on the SCO behavior. In this context, herein we present a novel family of mononuclear octahedral FeII complexes with formula cis- [Fe(bqen)(NCX)2], where bqen is the chelating tetradentate ligand N,N¿-bis(8-quinolyl)ethane-1,2-diamine and X = S, Se. Depending on the preparation method, these…
Electron-Sponge Behavior, Reactivity and Electronic Structures of Cobalt-Centered Cubic Co9Te6(CO)8 Clusters
2008
Extended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]–/[3]2–/[3]3–/[3]4–/[3]5– regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]– containing salts…
A hybrid magnet with coexistence of ferromagnetism and photoinduced Fe(iii) spin-crossover
2011
International audience; The insertion of a [Fe(sal2-trien)]+ complex cation into a 2D oxalate network results in a hybrid magnet with coexistence of magnetic ordering and photoinduced spin-crossover (LIESST effect) in compound [FeIII(sal2-trien)][MnIICrIII(ox)3]*(CH2Cl2) (1). A complete photomagnetic characterization together with a detailed structural analysis of the low-spin (LS) and high-spin (HS) structures of 1 is presented in order to understand such unusual behavior. This very rare and unexpected property in a FeIII spin-crossover complex, has been attributed to the strong distortion exhibited by the metastable HS state. Furthermore, 1 has shown that, in contrast to what has been pre…