Magnonics concepts utilize spin-wave quanta (magnons) for information transmission, processing and storage. To convert information carried by magnons into an electric signal promises compatibility of magnonic devices with conventional electronic devices, that is, magnon spintronics . Magnons in inorganic materials have been studied widely with respect to their generation, transport and detection . In contrast, resonant spin waves in the room-temperature organic-based ferrimagnet vanadium tetracyanoethylene (V(TCNE) (x ≈ 2)), were detected only recently . Herein we report room-temperature coherent magnon generation, transport and detection in films and devices based on V(TCNE) using three different techniques, which include broadband ferromagnetic resonance (FMR), Brillouin light scattering (BLS) and spin pumping into a Pt adjacent layer. V(TCNE) can be grown as neat films on a large variety of substrates, and it exhibits extremely low Gilbert damping comparable to that in yttrium iron garnet. Our studies establish an alternative use for organic-based magnets, which, because of their synthetic versatility, may substantially enrich the field of magnon spintronics.

We describe the results of a study on the stabilities of pincer-type nickel complexes relevant to catalytic hydroalkoxylation and hydroamination of olefins, C-C and C-X couplings, and fluorination of alkyl halides. Complexes [(POCsp3 OP)NiX] are stable for X=OSiMe3 , OMes (Mes=1,3,5-Me3 C6 H2), NPh2, and CC-H, whereas the O(tBu) and N(SiMe3)2 derivatives decompose readily. The phenylacetylide derivative transforms gradually into the zero-valent species cis-[{κ(P),κ(C),κ(C')-(iPr2 POCH2 CHCH2 )}Ni{η(2),κ(C),κ(C')-(iPr2 P(O)CCPh)}]. Likewise, attempts to prepare [(POCsp3 OP)NiF] gave instead the zwitterionic trinuclear species [{(η(3) -allyl)Ni}2-{μ,κ(P),κ(O)-(iPr2 PO)4 Ni}]. Characterization of these two complexes provides concrete examples of decomposition processes that can dismantle POCsp3 OP-type pincer ligands by facile C-O bond rupture. These results serve as a cautionary tale for the inherent structural fragility of pincer systems bearing phosphinite donor moieties, and provide guidelines on how to design more robust analogues.

Guest molecules may endow porous materials with new or enhanced properties as well as functions. Here, a porous hydrogen-bonded organic framework (HOF) constructed from a 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 regulate HOF's luminescence. Interestingly, acetic acid as a guest endowed HOF materials with longer emission wavelengths and triggered the responses to mechanical force stimuli. Under shear force, an obvious blueshift in emission spectra was observed because of the loss of free guests and the conversion of πstacking model. Further blue-shifted emission appeared while the bound guests were completely removed by heating. Mechanofluorochromic HOF materials could be regenerated through recrystallization and adsorbing guest. Conversely, HOFs with other guests and activated HOFs only resulted in a slight change in their fluorescence behaviors after force stimuli.

This contribution presents evidence for new pathways manifested in the reactions of the phenylhydrosilanes PhnSiH4-n with the 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 with 1-OSiMe3 to eliminate the disilyl ethers Ph(n)H(3-n)SiOSiMe3 (n = 1 or 2) and generate the nickel hydride species 1-H. Subsequent reaction of the latter with more substrate formed corresponding nickel silyl species 1-SiPhH2 or 1-SiPh2H and generated multiple Si-containing products, including disilanes and redistribution products. The reaction of 1-OSiMe3 with excess Ph2SiH2/Ph2SiD2 revealed a net KIE of ca. 1.3-1.4 at room temperature. Treating 1-OSiMe3 with excess Ph3SiH also gave 1-H and the corresponding disilyl ether Ph3SiOSiMe3, but this reaction also generated the new siloxide 1-OSiPh3 apparently via an unconventional σ-bond metathesis pathway in which the Ni center is not involved directly. The reaction of excess PhSiH3 and 2-OSiMe3 gave polysilanes of varying solubilities and molecular weights; NMR investigations showed that these polymers arise from Ni(0) species generated in situ from the reductive elimination of the highly reactive hydride intermediate, 2-H. The stoichiometric reactions of 2-OSiMe3 with Ph2SiH2 and Ph3SiH gave, respectively, siloxides 2-OSiPh2(OSiMe3) and 2-OSiPh3. Together, these results demonstrate the strong influence of pincer backbone and hydrosilane sterics on the different reactivities of 1-OSiMe3 and 2-OSiMe3 toward Ph(n)SiH(4-n) (dimerization, polymerization, and redistribution vs formation of new siloxides). The mechanisms of the reactions that lead to the observed Si-O, Si-C, and Si-Si bond formations are discussed in terms of classical and unconventional σ-bond metathesis pathways.

A dumbbell-shaped compound (TPAD) with four 2,4-diaminotriazine moieties as H-bond units and a benzene ring as a bridge group was found to form hydrogen-bonded organic frameworks (HOFs) with strong cyan fluorescence. An energy acceptor, 6,6′,6″, 6‴-(((benzo[c][1,2,5]thiadiazole-4,7-diylbis-(4,1phenylene))bis(azanetriyl))tetrakis(benzene-4,1-diyl))tetrakis-(1,3,5-triazine-2,4-diamine) (BTAD), with the same molecular skeleton as TPAD and a longer emission wavelength could homogeneously distribute within the framework of TPAD through occupying the locations of TPAD. As a result, two-component HOFs (TC-HOFs) were formed. The nonradiative energy transfer from TPAD as the donor to BTAD as the acceptor happens within frameworks owing to the efficient spectral overlap between the emission of TPAD and the absorption of BTAD. Moreover, the emission wavelengths and colors of TC-HOFs could be easily and continuously modulated by the content of the acceptor. The fluorescence color changed from cyan to orange when the content of BTAD gradually increased. This finding affirms that TC-HOFs with continuously adjustable composition can be constructed from two molecules with the same molecular skeleton, and highly efficient nonradiative energy transfer may happen in porous TC-HOFs. To the best of our knowledge, these TC-HOFs are the first example of TC-HOFs involved in energy transfer.

Rare earth metal complexes incorporating non-Cp type of ligands have attracted much attention since their interesting structural features and applications in molecular catalysis such as alkene and lactide polymerization reactions and intramolecular hydroamination of alkenes. 1 A number of bulky organic ligands have been employed for the stabilization of well-defined rare earth metal alkyls, amides, and alkoxides. In polymerization reactions, aluminum alkyls and aluminoxanes are frequently used as cocatalysts. 2 Consequently, the studies on the reactions of rare earth metal complexes with aluminum complexes have been extensively performed for the understanding polymerization mechanism. 3 An alternative approach for the investigation of oxo-bridged aluminumÀgroup 4 metal complexes indicated that these compounds are not only excellent for the polymerization reactions with low Al/Zr ratios but also display interesting structural features as indicated by the large AlÀOÀM angles and short MÀO bond lengths. 4 Inspired by these successful results, we are interested in the synthesis, characterization, and lactide polymerization behaviors of oxo-bridged aluminumÀrare earth metal (AlÀOÀLn) complexes. The known oxo-bridged AlÀOÀLn complexes are very limited and only confined to those containing Cp 2 Ln and β-diketiminato-Ln fragments. 5 Bimetallic AlÀOÀLn complexes possessing a reactive LnÀE σ-bond (E = CR 3 , NR 2 , OR), to the best our knowledge, have not been reported so far.Ring-opening polymerization (ROP) of lactide with welldefined metal complexes has been one of the recent focuses for the preparation of biodegradable polylactides. 6 Both rare-earth metal and aluminum complexes have been investigated as catalysts for the ROP. By incorporating suitable ancillary ligands, aluminum alkoxides exhibit relatively low rate but well-controlled stereochemistry over the polymerization reactions. 7 In contrast, rare-earth metal complexes generally display remarkable high activity. 8 It has been recently shown that several lanthanide complexes initiate the polymerization of rac-lactide in stereospecific manners. 9 However, oxo-bridged AlÀLn complexes have not been explored as ROP catalysts. Recent studies have revealed that aluminum hydroxides can function as building blocks for the synthesis of oxo-bridged heterometallic complexes. 4,5,10 We and others have previously reported several routes to prepare organoaluminum hydroxides that are stabilized by the bulky β-diketiminato ligand L (HC[(CMe)(NAr)] 2 , Ar = 2,6-iPr 2 C 6 H 3 ). 4a,11 Herein, we report on the synthesis and characterization of novel heterobimetallic AlÀOÀLn alkyls and aloxides, prepared by alkane elimination reactions of LAl(OH)(CPhCHPh) (1) with Ln (Ln = Y, Sm) alkyls. In addition, lactide polymerization reactions with these complexes have also been investigated.

Reaction of Me 4 C 5 H-SiMe 2 -NC 4 H 4 with Yb[N-(SiMe 3 ) 2 ] 2 (THF) 2 yielded a new type of ansa-sandwich divalent lanthanide amide (Me 4 C 5 -SiMe 2 -NC 4 H 4 )YbN-(SiMe 3 ) 2 ( 2), in which the Yb atom is η 5 -coordinated to both the C 5 and C 4 N rings. 2 rapidly reacted with dioxygen to give a dinuclear trivalent ytterbium species via intramolecular C-H and Si-N bond oxygenation reactions.

The synthesis and structural characterization of monomeric and linear polymeric divalent samarium complexes as well as their related trivalent species supported by an (imino)pyrrolide ligand are described. The divalent samarium 2-(N-arylamino)pyrrolide complex [NN]2Sm(THF)2 (1) was prepared by the reaction of SmI2(THF)2 with 2 equiv of [NN]K ([NN] = [2-(2,6-iPr2C6H3NCH)-5-tBuC4H2N]−) in THF. Upon treatment of 1 with dry oxygen, the oxo-bridged dimer [NN]2Sm(μ-O)Sm[NN]2 (2) was generated. Reaction of [NN]2SmCH2SiMe3 (3) with 3 equiv of AlEt3 in n-hexane gave the samarium aluminate [NN]2Sm(μ-Et)2AlEt2 (4). Reduction of 4 with potassium in toluene yielded the linear polymeric species {[NN]2SmAlEt4K(C7H8)} n (5). Compounds 1, 2, 4, and 5 have been characterized by X-ray single-crystal analysis. 5 features a linear polymeric structure, in which the potassium ion links the neighboring monomeric samarium moieties via η2 and η5 coordination to the pyrrolide rings in the two different units, with one toluene molecule and one of the ethyl groups of the [AlEt4] anion being also η2 coordinated to the potassium to complete its coordination sphere.