We report persistent chiral organic mono- and diradical cations based on bicarbazole molecular design with an unprecedented stability dependence the type of chirality, namely, axial versus helical. An unusual chemical was observed for sterically unprotected radical in comparison monocarbazole helical ones. Such results were experimentally theoretically investigated, revealing inversion energy singly occupied orbital (SOMO) highest (doubly) (HOMO) both monoradicals along a subtle difference...

Two 1,1,4,4-tetracyanobutadiene (TCBD) derivatives were prepared by [2+2]cycloaddition-retroelectrocyclization from ynamides bearing either a pyrene (1) or perylene unit (2). In addition to panchromatic absorptions in 2, the solid state, both compounds unexpectedly display NIR photoluminescence that could be detected up about 1350 nm.

The photoluminescent stimuli-responsive properties of two crystalline polymorphs with the formula (PPh4)2[Cu2I4] are reported. Distinct luminescence exhibited by these ionic copper iodide compounds blue or yellow emission, and original thermochromism mechanochromism demonstrated. While one polymorph displays contrasted temperature-dependent emission properties, other shows great modification its upon mechanical solicitation. establishment structure–properties relationships, supported a...

Abstract 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 single‐crystal X‐ray diffraction. The emission properties of the hybrids investigated as dry powders in various solvents one photon two absorption leading to a O 2 concentration dependent luminescence color for Mo based hybrid.

The Article presents the synthesis, structure, and bonding of a series neutral linear sandwich compounds with cyclononatetraenyl (Cnt) ligand divalent lanthanides. These account for emergence lanthanidocene in reference to ferrocene uranocene. synthetic strategy uses solubility difference between two conformational isomers ligand, as well isomerization induced by solvent coordination, yielding isomorphous isostructural rigorously complexes. molecular structures feature Cnt-Ln-Cnt angle 180°...

Luminescent mechanochromic materials exhibiting reversible changes of their emissive properties in response to external mechanical forces are currently emerging as an important class stimuli-responsive because promising technological applications. Here, we report on the luminescence a [Cu4I4(PPh3)4] copper iodide cluster presenting chair geometry, being isomer most common cubane form. This molecular formulated [Cu4I4(PPh3)4]·2CHCl3 (1) exhibits highly contrasted emission manual grinding,...

We report a new molecular design to afford persistent chiral organic open-shell systems with configurational stability and an inversion in energy of the singly occupied orbital (SOMO) highest doubly (HOMO) for both mono- diradical states. The unpaired electron delocalization within designed extended helical π-conjugated is crucial factor reach chemical stabilities, which not obtained using classical steric protection approach. unique features monoradicals allow exploration intramolecular...

A dinuclear metallacycle assembled from a bispyridyl dithienylethene linker and highly anisotropic dysprosium based Single Molecule Magnet (SMM) shows magnetic hysteresis at 1.8 K together with photoisomerization in single crystals (SC). The impact of photoswitching on the SMM behavior is evidenced related to specific organization units.

The tailoring of the coordination chemistry around f-element centers is a crucial step for development compounds with slow magnetic relaxation, including single-molecule magnets (SMMs), which have great potential in molecular spintronics and future quantum computing devices. Lanthanide ions are particularly interesting because predominant electrostatic model their bonding allows rationalizing symmetry. However, to best our knowledge, redox properties lanthanides not taken into account design...

We report herein P(III)-directed C–H bond alkenylation of (dialkyl)- and (diaryl)biarylphosphines using internal alkynes. Chloride-free [Rh(OAc)(COD)]2 acts as a better catalyst than commercially available [RhCl(COD)]2. Conditions were developed to control the mono- difunctionalization depending on alkyne stoichiometry. One these novel bisalkenylated (dialkyl)biarylphosphines was employed for preparation palladium(II) complex, some functionalized ligands outperformed their corresponding...

Abstract A 1D coordination compound made of a photochromic dithienylethene linker and [Dy(Tp 2−py )F] + units (with Tp =tris(3‐(2‐pyridyl)pyrazolyl)hydroborate) having tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate counterions is reported. Full photoconversion from the closed isomer to open within single crystals allow for monitoring transformation by photocrystallography. Magnetic slow relaxation as well magnetic hysteresis are observed can be both modulated upon light irradiation....

Capozzi's groundbreaking work in 1982 introduced a fascinating reaction involving highly reactive tertiary aliphatic cations and silylated alkynes. This provided an innovative solution to the challenge of coupling fully substituted fragment with alkyne moiety. Building upon pioneering efforts, we started extensive exploration conditions expand initial scope this reaction. Through meticulous control parameters, uncovered capable accommodating various functional groups, thereby enhancing...

The synthesis of a [7]helicene bromide derivative with two fused 2,1,3‐thiadiazole heterocycles (TD[7]Br) and comprehensive study its photophysical chiroptical characteristics are presented along comparison to 9‐bromo‐carbo[7]helicene ([7]Br) 3,15‐dibromo‐carbo[6]helicene ([6]Br). integration bromine heavy atom onto helicene backbone facilitates efficient singlet‐to‐triplet conversion allowing us investigate the resulting fluorescence phosphorescence properties. Steady‐state features systems...

The unique combination of a divalent organolanthanide fragment, Cp*2Yb, with bipyrimidine (bipym) and palladium bis-alkyl PdMe2, allows the rapid formation stabilization PdIV tris-alkyl moiety after oxidative addition MeI. crucial role fragment is demonstrated by substitution bipym 4,5,9,10-tetraazaphenanthrene ligand, which drastically modifies electronic structure tunes stability species.

A mechanochromic luminescent copper iodide cluster is reported whose luminescence exalted in response to mechanical stress. The underlying mechanism has been investigated along with the preparation of mechanically responsive films.

In this article, we report on a series of cyclometalated chloro- and alkynyl-platinum(II) complexes bearing various tridentate N^C^N-cyclometalated ligands derived from 1,3-bis(pyrimidin-2-yl)benzene. The X-ray crystal structures two were determined other DFT-calculated. Electrochemical DFT-computational studies suggest ligand-centred reduction the R1-substituted N^C^N ligand, whereas oxidation likely occurs either Pt-phenylacetylide moiety and/or ligand. CH2Cl2 solution at room temperature,...

We report the straightforward one-pot synthesis of novel 5- or 6-membered P-heterocycles featuring an internal ylidic bond: P-containing acenaphthylenes and phenanthrenes. The stability compounds tolerates post-functionalization through direct arylation to introduce electron-rich/poor substituents synthetic strategy is also compatible with preparation more elaborate polyaromatic scaffolds such as acenes helicenes. Using a joint experimental (X-ray analysis, optical redox properties)...

1,1,4,4-Tetracyanobutadienes (TCBDs) bearing a large diversity of fluorophores were prepared following multi-step synthesis. In crucial last step, all compounds obtained from the corresponding ynamides, which particularly suitable for formation TCBDs in presence tetracyanoethylene via [2+2] cycloaddition/retroelectrocyclization step (CA-RE). Several fluorenyl derivatives addition to phenanthrenyl and terphenyl ones provided ynamide-based affording remarkable emission properties covering...

An improvement in the catalytic enantioselective allylboration of isatins with 2-allyl-1,3,2-dioxaborolane presence chiral BINOL derivatives is reported, offering an efficient one-step access to enantioenriched N-unprotected 3-allyl-3-hydroxy-2-oxindoles. This process also effective for crotylboration reaction enantiomeric ratios (er) up 97:3, as well asymmetric synthesis homopropargylic alcohols via allenyl addition indoline-2,3-diones. Origins high enantioselectivity BINOL-catalyzed were...

The base-free divalent samarium complex Cptt2Sm (1; Cptt = 1,3-(tBu)2(C5H3)) has been synthesized in diethyl ether by salt metathesis of SmI2. Crystals 1 suitable for X-ray study have obtained sublimation at 116 °C under reduced pressure. dissolution thf and pyridine solution leads to the solvent adducts Cptt2Sm(thf)2 (3) Cptt2Sm(py) (4), respectively, while drying 3 pressure yields CpttSm(thf) (5). reaction CO2 with complexes (1) Cpttt2Sm (2; Cpttt =1,2,4-(tBu)3(C5H2)) clean formation...

Oxyallyl cations are prepared in situ from readily available α-tosyloxy ketones and act as transient electrophilic partners (3 + 3) cycloaddition with nitrones. Under mild conditions, this method provides a chemoselective diastereoselective route to polysubstituted 1,2-oxazinanes. A stepwise process is proposed rationalize the diastereoselectivity of transformation.

The synthesis and photophysical chiroptical properties of novel aza[n]helicenes (6a–d, 10a,b, n = 4–7) substituted with one or two 2-pyridyl groups are described. preparation was performed via an adapted Mallory reaction using aromatic imines as precursors. obtained class helical 2,2′-bipyridine ligands then coordinated to Ru(bipy)22+ units, thus affording the first diastereomerically enantiomerically pure [RuL(bipy)2]2+ (11a,c, L 6a,c) [Ru2L′(bipy)4]4+ (12, L′ 10b) complexes. topology...

A series of phosphorescent platinum(II) complexes containing various phenyldiazine-type bidentate N^C ligands have been successfully synthesized and characterized. Structural modifications made to cyclometalating regarding the nature diazine ring (pyrimidine, pyrazine quinazoline), substituent groups at C4 position pyrimidine (OCH3, CF3) EDGs para Pt atom Ph, NPh2, carbazol). In addition, electronic properties azaheterocyclic ancillary ligand modulated in this (pyridine, 4-methoxy-pyridine...

Abstract The first molecular Tm II luminescence measurements are reported along with rare magnetic, X and Q bands EPR studies. Access to simple soluble divalent lanthanide complexes is highly sought for small‐molecule activation studies organic transformations using single‐electron transfer processes. However, owing their low stability propensity disproportionate, these hard synthetize electronic properties therefore almost unexplored. Herein we present the synthesis of [Tm(μ‐OTf) 2 (dme) ]...