Following a previous microbial inoculation, plants can induce broad-spectrum immunity to pathogen infection, a phenomenon known as systemic acquired resistance (SAR). SAR establishment in Arabidopsis thaliana is regulated by the Lys catabolite pipecolic acid (Pip) and flavin-dependent-monooxygenase1 (FMO1). Here, we show that elevated Pip is sufficient to induce an FMO1-dependent transcriptional reprogramming of leaves that is reminiscent of SAR. In planta and in vitro analyses demonstrate that FMO1 functions as a pipecolate N-hydroxylase, catalyzing the biochemical conversion of Pip to N-hydroxypipecolic acid (NHP). NHP systemically accumulates in plants after microbial attack. When exogenously applied, it overrides the defect of NHP-deficient fmo1 in acquired resistance and acts as a potent inducer of plant immunity to bacterial and oomycete infection. Our work has identified a pathogen-inducible L-Lys catabolic pathway in plants that generates the N-hydroxylated amino acid NHP as a critical regulator of systemic acquired resistance to pathogen infection.
A series of easily accessible linear N-heterocyclic carbene (NHC) copper(I) complexes, bearing pyridine (py) and its derivatives as chromophore ligands, are barely emissive in the single-crystalline solid state. However, their powders, neat films, and dilute doped films of poly(methyl methacrylate) (PMMA; 1–10%) show very intense blue-to-blue-green photoluminescence with remarkable quantum yields φ of up to 87% and microsecond lifetimes, indicative of triplet states being involved. These luminescence properties are similar to trigonal coordinated NHC copper(I) bis(pyridine) complexes, which we have also isolated and characterized with respect to their structures and photophysics. Our spectroscopic and theoretical studies provide detailed insight into the nature of the luminescence enhancing effect of the linear two-coordinated copper(I) compounds, which is based on the formation of Cu–F interactions between the BF4 – anions and [Cu(NHC)(2-R-py)]+ (R = H, Me, Ph) cations. These interactions are absent in the single crystals but lead to a distorted ground-state structure in the precipitated powders or in PMMA films, giving rise to high k r. In addition, we found that our linear copper(I) complexes exhibit mechanochromic luminescence because grinding of the single crystals leads to enhanced emission intensity. In light of the recently reported cation–anion contact-induced mechanochromic luminescence of two-coordinated copper(I) complexes, this study supports the generality of this new mechanism for the design of mechanoresponsive phosphorescent materials.
The sterically demanding carbene ITr (N,N′bis(triphenylmethyl)imidazolylidene) was used as a ligand for the preparation of luminescent copper(I) complexes of the type [(ITr)Cu(R-pyridine/R′-quinoline)]BF 4 (R = H, 4-CN, 4-CHO, 2,6-NH 2 , and R′ = 8-Cl, 6-Me). The selective formation of linear, bis(coordinated) complexes was observed for a series of pyridine and quinoline derivatives. Only in the case of 4-cyanopyridine a one-dimensional coordination polymer was formed, in which the cyano group of the cyanopyridine ligand additionally binds to another Cu atom in a bridging manner, thus leading to a trigonal planar coordination environment. In contrast, employing sterically less demanding monotrityl-substituted carbene 3, no (NHC)Cu-pyridine complexes could be prepared. Instead, a bis-carbene complex [(3) 2 Cu]PF 6 was obtained which showed no luminescence. All linear pyridine/quinoline coordinated complexes show weak emission in solution but intense blue to orange luminescence doped with 10% in PMMA films and in the solid state either from triplet excited states with unusually long lifetimes of up to 4.8 ms or via TADF with high radiative rate constants of up to 1.7 × 10 5 s −1 at room temperature. Combined density functional theory and multireference configuration interaction calculations have been performed to rationalize the involved photophysics of these complexes. They reveal a high density of low-lying electronic states with mixed MLCT, LLCT, and LC character where the electronic structures of the absorbing and emitting state are not necessarily identical.
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