title: Metalation of tetraphenylporphyrin with nickel on a TiO2(110)-1 × 2 surface.
abstract: The in situ metalation of tetraphenylporphyrin (2HTPP) with Ni on the reconstructed TiO2(110)-1 × 2 surface, resulting in the formation of adsorbed nickel(II)-tetraphenylporphyrin (NiTPP), has been investigated by synchrotron radiation photoemission spectroscopy (SRPES), scanning tunnelling microscopy (STM) and ab initio Density Functional Theory (DFT) calculations. The metalation can be realized at room temperature irrespective of the deposition order of Ni and 2HTPP, which however leads to different metalation degrees. Increasing the substrate temperature or Ni : 2HTPP ratio results in higher metalation degree, which ultimately reaches its limit at ∼85% (Ni : 2HTPP = 3 : 1) and ∼49% (Ni : 2HTPP = 1 : 1) for post- and pre-deposition of Ni, respectively. The reaction from 2HTPP to NiTPP is accompanied by changes of the molecular adsorption conformation and the adsorption site from a tilted two-lobed feature on added Ti2O3 rows to a four-lobed feature on top of troughs or cross-links of the TiO2(110)-1 × 2 surface. This interpretation of the STM data is supported by DFT-based STM simulations.
authors.affiliation: National Synchrotron Radiation Laboratory and Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China, Hefei, 230029, P. R. China.
authors.forename: Cici
authors.initials: C
authors.lastname: Wang
authors.affiliation: National Synchrotron Radiation Laboratory and Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China, Hefei, 230029, P. R. China.
authors.forename: Qitang
authors.initials: Q
authors.lastname: Fan
authors.affiliation: National Synchrotron Radiation Laboratory and Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China, Hefei, 230029, P. R. China.
authors.forename: Yong
authors.initials: Y
authors.lastname: Han
authors.affiliation: ESISNA Group, Dept. Surfaces, Coatings and Molecular Astrophysics, Institute of Material Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz, 3, 28049, Madrid, Spain.
authors.forename: José I
authors.initials: JI
authors.lastname: Martínez
authors.affiliation: ESISNA Group, Dept. Surfaces, Coatings and Molecular Astrophysics, Institute of Material Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz, 3, 28049, Madrid, Spain.
authors.forename: José A
authors.initials: JA
authors.lastname: Martín-Gago
authors.affiliation: National Synchrotron Radiation Laboratory and Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China, Hefei, 230029, P. R. China.
authors.forename: Weijia
authors.initials: W
authors.lastname: Wang
authors.affiliation: National Synchrotron Radiation Laboratory and Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China, Hefei, 230029, P. R. China.
authors.forename: Huanxin
authors.initials: H
authors.lastname: Ju
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35032, Marburg, Germany.
authors.forename: J Michael
authors.initials: JM
authors.lastname: Gottfried
authors.affiliation: National Synchrotron Radiation Laboratory and Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China, Hefei, 230029, P. R. China.
authors.forename: Junfa
authors.initials: J
authors.lastname: Zhu