A suitable technology for the preparation of graphene based on versatile wet chemistry is presented for the first time. The protocol allows the wet chemical synthesis of graphene from a new form of graphene oxide that consists of an intact hexagonal σ-framework of C-atoms. Thus, it can be easily reduced to graphene that is no longer dominated by defects.

We investigated the coordination self-assembly and metalation reaction of Cu with 5,10,15,20-tetra(4-pyridyl)porphyrin (2HTPyP) on a Au(111) surface by means of scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. 2HTPyP was found to interact with Cu through both the peripheral pyridyl groups and the porphyrin core. Pairs of pyridyl groups from neighboring molecules coordinate Cu(0) atoms, which leads to the formation of a supramolecular metal-organic coordination network. The network formation occurs at room temperature; annealing at 450 K enhances the process. The interaction of Cu with the porphyrin core is more complex. At room temperature, formation of an initial complex Cu(0)-2HTPyP is observed. Annealing at 450 K activates an intramolecular redox reaction, by which the coordinated Cu(0) is oxidized to Cu(II) and the complex Cu(II)TPyP is formed. The coordination network consists then of Cu(II) complexes linked by Cu(0) atoms; that is, it represents a mixed-valence two-dimensional coordination network consisting of an ordered array of Cu(II) and Cu(0) centers. Above 520 K, the network degrades and the Cu atoms in the linking positions diffuse into the substrate, while the Cu(II)TPyP complexes form a close-packed structure that is stabilized by weak intermolecular interactions. Density functional theory investigations show that the reaction with Cu(0) proceeds via formation of an initial complex between metal atom and porphyrin followed by formation of Cu(II) porphyrin within the course of the reaction. The activation barrier of the rate limiting step was found to be 24-37 kcal mol(-1) depending on the method used. In addition, linear coordination of a Cu atom by two CuTPyP molecules is favorable according to gas-phase calculations.

Temperature-dependent chemical and structural changes of a submonolayer of 2H-tetraphenylporphyrin (2HTPP) on Cu(111) were studied with photoelectron spectroscopy (XPS/UPS) and scanning tunneling microscopy (STM). 2HTPP reacts with Cu atoms from the substrate to form copper(II)-tetraphenylporphyrin (CuTPP). This metalation reaction starts at about 400 K and was investigated at various temperatures up to 500 K. At room temperature, adsorbed 2HTPP adopts an orientation with the molecular plane parallel to the substrate; the same holds for its reaction product CuTPP after annealing to 400 K. In contrast, annealing at 450 K yields a tilted orientation of CuTPP, as indicated by STM and supported by C 1s XPS shifts and changes in the Cu(111) surface state. Subsequent annealing at 500 K restores a flat-lying orientation; however, the appearance of the complex in STM images differs from the original appearance of CuTPP. In summary, 2HTPP undergoes three irreversible transformations upon annealing on Cu(111), a metalation reaction to CuTPP followed by two intramolecular structural changes.

We address the dynamic behavior and the surface chemical bond of 2H-tetraphenylporphyrin (2HTPP) on Cu(111) around room temperature by variable-temperature scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) in ultrahigh vacuum. Between 280 and 345 K, the molecules predominantly display unidirectional diffusion along one of the three densely packed substrate AE110ae directions, which is attributed to a high site selectivity of the adsorbateÀsubstrate bond. Above 305 K, the diffusion direction is found to change occasionally by (120°. The activation barriers for the unidirectional diffusion and for rotation of the diffusion direction are determined to 0.71 ( 0.08 and 1.28 ( 0.12 eV, respectively. XPS shows that the iminic nitrogen atoms of 2HTPP interact strongly with the Cu surface. It is postulated that the local bonding situation is similar as in the initial complex (sitting-atop complex), which has previously been observed during the surface-confined in situ metalation of porphyrins.

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IntroductionThe self-assembly of porphyrins on well-defined surfaces is attracting considerable interest because it promises to create surface patterns with nanometer dimension that exhibit specific electronic, sensoric, optic, or catalytic functionality 1-3 or even interesting magnetic properties. 4,5 The ability of porphyrin to show self-organization and to accommodate metal atoms in their macrocycle is exploited, for instance, to form metal−organic frameworks or adsorbed layers for catalysis. [6][7][8][9] The selfassembly is mainly driven by noncovalent metal−organic coordination interactions, which is well-known and important in solution-based 3D supramolecular chemistry. [10][11][12][13][14][15] Porphyrin molecules have been adsorbed onto surfaces to form supramolecular networks from solution, [16][17][18][19] electrochemically 20,21 or by thermal evaporation under vacuum conditions. [22][23][24][25][26][27][28] While there is a rich literature on the electronic structure of these adsorbates, the surface adlayer structures have also been characterized with scanning force microscopy, scanning tunneling microscopy, or X-ray absorption near-edge structure analysis. 29 The rationale of such experiments on 2D structures has been to study the long-range interactions that determine the self-assembly processes. It has been demonstrated that the bottom-up fabrication of highly organized porphyrin layers, as well as of porphyrin-based multicomponent molecular entities, depends on the interplay of molecule−molecule and substrate−molecule interactions. Molecule−substrate interactions will set limits to the mobility of the adsorbed molecules and may alter the electronic structure of the absorbed molecules, or the electronic states at the surfaces may become locally perturbed by the adsorbate. 60 A consequence is that the established concepts of solution-based coordination chemistry cannot be applied without appropriate modification. The substrate thus becomes an additional parameter to control the adsorption energy of the molecules and, hence, their diffusivity at surfaces. An intriguing demonstration of this effect is the self-assembly of porphyrins, which are decoupled from their metal substrate by insulating NaCl layers of varying thickness. 23 The interaction was shown to be dependent on the NaCl layers, and the thicker the NaCl the weaker the interaction and the more delayed the onset of network formation. The occupation of the center ring of the porphyrin may affect the molecular adsorption at surfaces. As an example, free-base or Cu-incorporated porphyrin molecules show different arrangements along step edges on Cu(100) surfaces. While 2H-TBPP bridges over the step edges, Cu-TBPP sits on either side of step edges. 27 In contrast, no difference in the network architecture was found for differently metalated TPP on Ag(111). 57 Such a subtle dependence of adsorption site on metal incorporation, if fully understood, may become useful to control the self-assembly or the properties of the molecules on surfaces.The goal...

Hetero‐shaped thermoelectric (TE) generators (TEGs) can power the sensors used in safety monitoring systems of undersea oil pipelines, but their development is greatly limited by the lack of materials with both good shape‐conformable ability and high TE performance. In this work, a new ductile inorganic TE material, Ag20S7Te3, with high TE performance is reported. At 300–600 K, Ag20S7Te3 crystallizes in a body‐centered cubic structure, in which S and Te atoms randomly occupy the (0, 0, 1) site. Due to the smaller generalized stacking fault energy in the (101¯)[010] slip system, Ag20S7Te3 shows better ductility than Ag2S, yielding excellent shape‐conformability. The high carrier mobility and low lattice thermal conductivity observed in Ag20S7Te3 result in a maximum dimensionless figure of merit (zT) of 0.80 at 600 K, which is comparable with the best commercial Bi2Te3‐based alloys. The prototype TEG consisting of 10 Ag20S7Te3 strips displays an open‐circuit voltage of 69.2 mV and a maximum power output of 17.1 µW under the temperature difference of 70 K. This study creates a new route toward hetero‐shaped TEG.

The synthesis, structure, and reactivity of some organo-iron complexes with monodentate N-heterocyclic carbene (NHC) ligation were studied. Mononuclear ferrous complexes [(IEt) 2 FeR 2 ] (IEt = 2,5-diethyl-3,4-dimethylimidazol-1-ylidene, R = Me (2a), CH 2 TMS (2b)) and [(IPr)FeMes 2 ] (3, IPr = 2,5-diisopropyl-3,4-dimethylimidazol-1-ylidene) were prepared in good yields via salt elimination reactions of [(NHC) 2 FeCl 2 ] (1) with alkylation reagents. The interaction of 1 with PhLi gave a mixture of dinuclear complexes [Cl(IEt)Fe(IEt 0 ) 2 Fe(IEt)Cl] (4a) and [Ph(IEt)Fe(IEt 0 ) 2 Fe(IEt)Ph] (4b) (IEt 0 = 3-Et-4,5-Me 2 -2-ylideneimidazolyl anion), in which NÀC(ethyl) bond cleavage of the NHC ligand was involved. Complexes 2aÀ4b were characterized by 1 H NMR, elemental analyses, and single-crystal X-ray diffraction studies. Solution magnetism measurement by Evan's method revealed the high-spin electronic configuration for the mononuclear organo-iron(II) complexes 2a, 2b, and 3. Reactivity studies showed the tetrahedral complex 2a was inert toward many unsaturated organic substrates, whereas the trigonal-planar complex 3 could react with CO and carbodiimide Pr i NdCdNPr i to yield dimesityl ketone and [(IPr)Fe(Mes)(η 2 -Pr i NC(Mes)NPr i )] (5), respectively. Relevant to iron-catalyzed Kumada couplings, both complexes 2b and 3 were found reactive with PhI to yield the corresponding carbonÀcarbon bond formation products PhÀCH 2 TMS and PhÀMes.