Supporting Information for. Surface-Controlled Mono-/di-Selective Ortho C-H Bond Activation

Transcription

1 Supporting Information for Surface-Controlled Mono-/di-Selective Ortho C-H Bond Activation Qing Li, Biao Yang, Haiping Lin, Nabi Aghdassi, Kangjian Miao, Junjie Zhang, Haiming Zhang, Youyong Li, Steffen Duhm, Jian Fan and Lifeng Chi Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, 199 Ren'ai Road, Suzhou, , Jiangsu, P. R. China. 1, Self-assembly of THPB on Au(111) Surface After deposition of THPB on Au(111) held at room temperature, a regular self-assembly structure is formed as shown in S1a. In order to study the details of the self assembly structure, the DFT-optimized relaxed structure was obtained (Fig. S1b). DFT calculations reveal that the island is stabilized by the net hydrogen bonding between the hydroxyl groups. A simulated STM image based on the relaxed structure (Fig. S1c) is in nice agreement with the experimental observations and thus verifies the proposed structural model. Figure S1. The self-assembly structure of THPB on Au(111). (a), Representative STM image of the self-assembly structure of THPB on Au(111). I t = 20 pa, V b = 1.0 V. (b), STM image of the self-assembly structure superimposed by a DFT-optimized relaxed structural model. The gray, red and white balls represent the C, O and H atoms, respectively. (c), DFT-simulated STM image based on the structural model shown in (b). 2. DFT calculations of the deoxygenation reaction and the second ortho dehydrogenation. The calculation of transition state (TS) were performed with Climbing Image S1

2 Nudged-Elastic Band (CI-NEB) method. Three structural images were inserted between the initial and the final states along the reaction coordinates, as shown in Fig. S2 and S3. Figure S2. Five DFT calculated structural images along the reaction coordinate of the second dehydrogenation reaction on the Ag(111) and Au(111) surfaces. In the initial states, a metal ad-atom is sitting above a hollow site near the oxygen atom (highlighted with a red circle). As the reaction processes, the metal ad-atom tends to squeeze itself into the C-H bond. In the final states, metal ad-atoms form chemical bonds with the C and H atoms. S2

3 Figure S3. Five DFT calculated structural images along the reaction coordinate of deoxygenation reaction on the Ag(111) and Au(111) surfaces. In the initial states, a metal ad-atom is sitting above a hollow site near the oxygen atom (highlighted with a red circle). As the reaction processes, the metal ad-atom tends to squeeze itself into the C=O double bond. In the final states, metal ad-atoms form chemical bonds with the C and O atoms. 3, Evolution of the THPB self-assembly structures on Ag(111) Figure S4. Evolution of the THPB self-assembly structures on Ag(111). (a)-(c) Representative STM images of the self-assembly structures after RT depositing (a), 50 C annealing (b) and 120 C annealing (c). In Fig. 5b, an obvious shift was observed on the low energy peak. It shifts from ev at RT to ev at 50 C and to ev at 100 C. Actually, such S3

4 phenomenon is quite common and it can be ascribed to the change of local environment of the chemical species, induced by the evolution of the self-assembly phase 1-3. The evolution of the self-assembly phases was indeed observed by annealing the sample at different temperature during our experiments. As shown by Fig. S4, Deposition of THPB on Ag(111) kept at RT (Fig. 2a) forms a self-assembly structure, which differs slightly from its counterpart on Au(111) (Fig. S1). As supported by the RT O1s XPS spectra (Fig. 5b), such difference arises from the partial conversion of hydroxyls to carbonyls at RT. After 50 C annealing, a porous network was visible, which is a result of conversion of more hydroxyls to carbonyls. When all the hydroxyls were converted, a close packed self-assembly structure is formed. 4, Structural evolution of DHQP on Au(111) upon thermal annealing In order to demonstrate the generality of the surface-controlled selective C-H activation, the particular reaction behaviors of DHQP on both Au(111) and Ag(111) surfaces were investigated. The deposition of DHQP on Au(111) at a relative low temperature (270 ºC) predominantly leads to stripes (Fig. S5a). High-resolution STM images (Fig. S5b) reveal that the configuration of the phenyl rings resembles the polymerization of quaterphenyls on Cu(110) surface 4, suggesting an ortho-ortho coupling. Similar to the reaction behavior of THPB, a porous network on Au(111) is formed at a higher preparation temperature, as shown in Fig. S5c and S5d. Figure S5. Reaction products of DHQP on Au(111). (a,b) STM image after sample preparation at 270 C. (c,d) STM images after sample preparation at 320 C. Structural models are shown in the lower panel. 5, Cross-coupling of phenol derivatives on Au(111) and Ag(111) surfaces The DFT calculation indicates that the surface-controlled selective C-H activation reaction is due to the different O-M (M represents an Au or Ag atom) interaction after the initial phenol oxidation. Such a mechanism is independent of the chemical groups attached to the phenol, thus the hydroxyl group assisted C-H activation should not only be valid for homo-coupling but also for a cross-coupling of two different monomers. The cross-coupling of THPB and DHQP is indeed successfully achieved on both gold and silver surfaces with the same reaction selectivity. Figure S6a shows an STM image after co-deposition of THPB and DHQP onto a Au(111) sample at S4

5 320 C. In addition to the porous network, some seamless connections between THPB and DHQP monomers can be observed, thus indicating the occurence of cross-coupling. A similar behavior is also observed on Ag(111) surfaces (Fig. S6b) Figure S6. Cross-coupling on Au(111) and Ag(111) surfaces. (a) STM image of Au(111) after co-deposition of THPB and DHQP at a substrate temperature of 320 C. (b) STM image of Ag(111) after co-deposition of THPB and DHQP at a substrate temperature of 320 C. References: (1) Fischer, S.; Papageorgiou, A. C.; Lloyd, J. A.; Oh, S. C.; Diller, K.; Allegretti, F.; Klappenberger, F.; Seitsonen, A. P.; Reichert, J.; Barth, J. V. ACS Nano 2014, 8, (2) Giovanelli, L.; Ourdjini, O.; Abel, M.; Pawlak, R.; Fujii, J.; Porte, L.; Themlin, J.; Clair, S. J. Phys. Chem. C 2014, 118, (3) Yang, B.; Bjork, J.; Lin, H. P.; Zhang, X. Q.; Zhang, H. M.; Li, Y. Y.; Fan, J.; Li, Q.; Chi, L. F. J. Am. Chem. Soc. 2015, 137, (4) Sun, Q.; Zhang, C.; Kong, H. H.; Tan, Q. G.; Xu, W. Chem. Commun. 2014, 50, S5