Guest molecules may endow porous materials with new or enhanced properties as well functions. Here, a hydrogen-bonded organic framework (HOF) constructed from three-armed triphenylamine derivative is used to investigate how guests regulate photoluminescence and trigger force-stimuli response. It was found that guest solvents in pores might HOF's luminescence. Interestingly, acetic acid endowed HOF longer emission wavelengths triggered the responses mechanical force stimuli. Under shear...

A butterfly-shaped phenothiazine derivative, PTTCN, was synthesized to obtain pure organic porous crystals for the highly efficient absorptive separation of toluene (Tol) and methylcyclohexane (Mcy). Due presence three polar cyano groups nonplanar conformation, these molecules self-assembled into a hydrogen-bonded framework (X-HOF-5) with distinct cavities capable accommodating Tol through multiple hydrogen-bonding interactions. Upon solvent removal via heating, activated X-HOF-5 retained...

A dumbbell-shaped compound (TPAD) with four 2,4-diaminotriazine moieties as H-bond units and a benzene ring bridge group was found to form hydrogen-bonded organic frameworks (HOFs) strong cyan fluorescence. An energy acceptor, 6,6',6″,6‴-(((benzo[c][1,2,5]thiadiazole-4,7-diylbis-(4,1-phenylene))bis(azanetriyl))tetrakis(benzene-4,1-diyl))tetrakis(1,3,5-triazine-2,4-diamine) (BTAD), the same molecular skeleton TPAD longer emission wavelength could homogeneously distribute within framework of...

A linear distyrylanthracene derivative (DDATAn) with two diaminotriazine (DAT) groups acting as the hydrogen bond (H-bond) units was designed and synthesized in order to construct flexible organic porous crystals. H-bonds between DAT moieties helped molecules a double interpenetrated two-dimensional layer, stacking layers provided H-bonded framework (X-HOF-3) one-dimensional solvent channels. When X-HOF-3 placed contact methanol, fluorescent colors of HOF exhibited an apparent bathochromic...

A nonplanar phenothiazine derivative with three cyano moieties (PTTCN) is designed and synthesized to achieve functional crystals for absorptive separation of benzene cyclohexane. PTTCN can crystallize into two kinds different fluorescence colors in solvent systems. The molecules are stereo isomeric forms nitrogen, quasi axial (ax), equatorial (eq). blue ax form may selectively adsorb by a single-crystal-to-single-crystal (SCSC) transformation, but separated from benzene/cyclohexane...

This contribution presents evidence for new pathways manifested in the reactions of phenylhydrosilanes PhnSiH4-n with pincer complexes (POCsp(2)OP)Ni(OSiMe3), 1-OSiMe3, and (POCsp(3)OP)Ni(OSiMe3), 2-OSiMe3 (POCsp(2)OP = 2,6-(i-Pr2PO)2C6H3; POCsp(3)OP (i-Pr2POCH2)2CH). Excess PhSiH3 or Ph2SiH2 reacted 1-OSiMe3 to eliminate disilyl ethers Ph(n)H(3-n)SiOSiMe3 (n 1 2) generate nickel hydride species 1-H. Subsequent reaction latter more substrate formed corresponding silyl 1-SiPhH2 1-SiPh2H...

Abstract We describe the results of a study on stabilities pincer‐type nickel complexes relevant to catalytic hydroalkoxylation and hydroamination olefins, CC CX couplings, fluorination alkyl halides. Complexes [(POC sp3 OP)NiX] are stable for X=OSiMe 3 , OMes (Mes=1,3,5‐Me C 6 H 2 ), NPh CCH, whereas O( t Bu) N(SiMe ) derivatives decompose readily. The phenylacetylide derivative transforms gradually into zero‐valent species cis ‐[{κ P ,κ C′ ‐( i Pr POCH CHCH )}Ni{η P(O)CCPh)}]. Likewise,...

This report describes the reactivities of POCOP-type pincer complexes nickel bearing a trimethylsiloxide ligand. The complex {κP,κC,κP-2,6-(i-Pr2PO)2C6H3}Ni(OSiMe3) (1-OSiMe3) reacts with 2,4,6-Me3-C6H2OH (MesOH) to give stable derivative 1-OMes, whereas corresponding tert-butoxide could not be prepared. Reaction 1-OSiMe3 and its aliphatic analogue {κP,κC,κP-(i-Pr2POCH2)2CH}Ni(OSiMe3) (2-OSiMe3) Ph3SiOH led facile formation protonolysis products 1-OSiPh3 2-OSiPh3. Treating or 2-OSiMe3...

It has been found that the separation selectivity of hydrogen-bonded organic frameworks for haloalkanes is closely associated with extent micro-structural changes during guest adsorption, where a smaller alteration favors higher selectivity.

Abstract This contribution describes the reactivities of CO 2 , CO, O and ArNC with pincer‐type complexes [(κ P ,κ C P′ ‐POC OP)NiX] (POC OP=(R POCH ) CH; R= i Pr; X=OSiMe 3 NArH; Ar=2,6‐ Pr 6 H ). Reaction amido derivative leads to a simple insertion into NiN bond give stable carbamate carbamoyl derivatives, respectively, pincer ligand backbone remaining intact in both cases. In contrast, analogous reactions siloxide produced kinetically labile products that either revert starting material...

Reactivity of a divalent ytterbium amide LYbN(SiMe3)2 (1, L = Me4C5-SiMe2-NC4H4) supported by pyrrolyl functionalized cyclopentadienyl ligand has been investigated. Reactions 1 with the element sulfur led to oxidation yield disulfide-bridged complex [LYbN(SiMe3)2]2(μ-η(2):η(2)-S2) (2) while that AgBPh4 resulted in LYb(BPh4) (3) along formation silver and N-N coupling product [N(SiMe3)2]2. phenol, phenylacetylene aniline corresponding aryloxide [LYb(μ-OAr(1))]2 (4, Ar(1) 2,6-tBu2-4-MeC6H2),...

The synthesis and structural characterization of monomeric linear polymeric divalent samarium complexes as well their related trivalent species supported by an (imino)pyrrolide ligand are described. 2-(N-arylamino)pyrrolide complex [NN]2Sm(THF)2 (1) was prepared the reaction SmI2(THF)2 with 2 equiv [NN]K ([NN] = [2-(2,6-iPr2C6H3N═CH)-5-tBuC4H2N]−) in THF. Upon treatment 1 dry oxygen, oxo-bridged dimer [NN]2Sm(μ-O)Sm[NN]2 (2) generated. Reaction [NN]2SmCH2SiMe3 (3) 3 AlEt3 n-hexane gave...

Reaction of the aluminum hydroxide LAl(OH)[C(Ph)CH(Ph)] (1, L = HC[(CMe)(NAr)](2), Ar 2,6-iPr(2)C(6)H(3)) with Y(CH(2)SiMe(3))(3)(THF)(2) yielded oxo-bridged heterobimetallic yttrium dialkyl complex LAl[C(Ph)CH(Ph)](μ-O)Y(CH(2)SiMe(3))(2)(THF)(2) (2). Alkane elimination reaction 2 2-(imino)pyrrole [NN]H ([NN]H 2-(ArN═CH)-5-tBuC(4)H(2)NH) afforded monoalkyl LAl[C(Ph)CH(Ph)] (μ-O)Y(CH(2)SiMe(3))[NN](THF)(2) (5). Alternatively, 5 can be prepared in high yield by 1 [NN]Y(CH(2)SiMe(3))(2)(THF)(2)...

To mitigate the microbiologically influenced corrosion of metallic components serving in marine environments, an innovative Ag nanoparticle (AgNP)/NbC nanocomposite coating was synthesized using a double glow discharge plasma method. The composed nanoparticles together with NbC nanocrystals embedded amorphous carbon (a-C) matrix. incorporation into played significant role determining both grain size and crystallographic texture phase, as well bonding state species surface morphology coating....

Reaction of Me4C5H-SiMe2-NC4H4 with Yb[N(SiMe3)2]2(THF)2 yielded a new type ansa-sandwich divalent lanthanide amide (Me4C5-SiMe2-NC4H4)YbN(SiMe3)2 (2), in which the Yb atom is η5-coordinated to both C5 and C4N rings. 2 rapidly reacted dioxygen give dinuclear trivalent ytterbium species via intramolecular C−H Si−N bond oxygenation reactions.

Charge-transfer (CT) complexes of 4,4′-bis(9H-carbazol-9-yl)-1,1′-biphenyl (CBP) and three acceptors emitted cyan, green, orange fluorescence, lower LUMO energy levels the promoted longer emission wavelengths. Moreover, they could reversibly convert their luminescent colors under force then fuming by chlorinated hydrocarbon solvents. Amazingly, acetonitrile vapor annealing might decompose CT to form a pure CBP crystalline phase, which induced sharp changes in fluorescence colors. As result,...

Hexacyanobutadiene (HCBD) and M(CO)x (M = V, x 6; Fe, 5) react in CH2Cl2 to form new organic-based magnets of M[HCBD]2·z(CH2Cl2) composition. Analysis the IR spectrum [M V: ν(CN) 2193 2116 cm–1 (fwhh ∼400 cm–1); Fe: 2196 2145 ∼150 cm–1)] suggests that HCBD is reduced radical anion, [HCBD]•–, broadness multiple variable nitriles sites are coordinated V(II), leading a complex mixture magnetic couplings behaviors deviate from paramagnetic behavior below K, frustrated magnet with Tc ≈ 9 K...

Abstract We describe the results of a study on stabilities pincer‐type nickel complexes relevant to catalytic hydroalkoxylation and hydroamination olefins, CC CX couplings, fluorination alkyl halides. Complexes [(POC sp3 OP)NiX] are stable for X=OSiMe 3 , OMes (Mes=1,3,5‐Me C 6 H 2 ), NPh CCH, whereas O( t Bu) N(SiMe ) derivatives decompose readily. The phenylacetylide derivative transforms gradually into zero‐valent species cis ‐[{κ P ,κ C′ ‐( i Pr POCH CHCH )}Ni{η P(O)CCPh)}]. Likewise,...

The reaction of 2,3,5,6-tetracyanopyridine (TCNPy) and Cr(C6H6)2 forms diamagnetic σ-[TCNPy]22− possessing a 1.572(3) Å intrafragment sp3–sp3 bond. This is in contrast to the structurally related 1,2,4,5-tetracyanobenzene 1,2,4,5-tetracyanopyrazine that form π-dimer dianions long, multicenter bonds.

The reaction of 2,3,5,6-tetracyanopyridine (TCNPy) with V(CO)6 in CH2 Cl2 forms new organic-based magnets V[TCNPy]x ⋅z (CH2 ) (x=2, 3) composition. Analysis the IR spectra suggests that TCNPy is reduced and coordinated to V(II) sites through nitriles. order as ferrimagnets 111 90 K Tc values for V[TCNPy]2 V[TCNPy]3 , respectively. Their respective remanent magnetizations coercive fields are 1260 250 emuOe mol(-1) 9 6 Oe at 5 K, they exhibit some spin-glass behavior.