Self-Metalation of 2H-Tetraphenylporphyrin on Cu(111) Studied with XSW: Influence of the Central Metal Atom on the Adsorption Distance

被引：38

作者：

Buerker, C. ^{[1
]}

Franco-Canellas, A. ^{[1
]}

Broch, K. ^{[1
]}

Lee, T. L. ^{[2
]}

Gerlach, A. ^{[1
]}

Schreiber, F. ^{[1
]}

机构：

[1] Univ Tubingen, Inst Angew Phys, Morgenstelle 10, D-72076 Tubingen, Germany

[2] Diamond Light Source, Didcot OX11 0DE, Oxon, England

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2014年 / 118卷 / 25期

关键词：

SURFACE-STRUCTURE DETERMINATION; INTERMOLECULAR INTERACTION; PORPHYRIN METALATION; AG(111); CONFORMATION; MOLECULES; CATALYSIS; AU(111); PTCDA; IRON;

D O I：

10.1021/jp503046w

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We present a systematic X-ray standing wave (XSW) study of the pi-conjugated organic compound 2H-tetraphenylporphyrin (2HTPP) and copper(II)-tetraphenylporphyrin (CuTPP) on Cu(111) at room and low temperatures. We exploit the feature of thermally activated self-metalation of 2HTPP to CuTPP to study the influence of the central metal atom on the bonding distance of the molecule to the substrate surface. Comparison between the average adsorption distances of the carbon and nitrogen atoms of 2HTPP reveals a distorted molecule with the nitrogen atoms being closer to the surface than the carbon ones on average. Additionally, the measured positions of the two chemically inequivalent types of nitrogen atoms (iminic and aminic) of 2HTPP indicate a distorted porphyrin ring. After the chemical reaction from 2HTPP to CuTPP at 500 K, no change of the adsorption distance of the carbon skeleton is seen, but the entire molecule becomes flattened. Despite the changes upon metalation, adsorption distances for both molecules show a strong interaction with the substrate in comparison to similar pi-conjugated molecules.

引用

页码：13659 / 13666

页数：8

共 49 条

[1] Highly efficient phosphorescent emission from organic electroluminescent devices [J].

Baldo, MA ;

O'Brien, DF ;

You, Y ;

Shoustikov, A ;

Sibley, S ;

Thompson, ME ;

Forrest, SR .

NATURE, 1998, 395 (6698) :151-154

[2] Homogeneous catalysis of electrochemical hydrogen evolution by iron(0) porphyrins [J].

Bhugun, I ;

Lexa, D ;

Saveant, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (16) :3982-3983

[3] Dynamics of molecular self-ordering in tetraphenyl porphyrin monolayers on metallic substrates [J].

Brede, Jens ;

Linares, Mathieu ;

Kuck, Stefan ;

Schwoebel, Joerg ;

Scarfato, Alessandro ;

Chang, Shih-Hsin ;

Hoffmann, Germar ;

Wiesendanger, Roland ;

Lensen, Roy ;

Kouwer, Paul H. J. ;

Hoogboom, Johan ;

Rowan, Alan E. ;

Broering, Martin ;

Funk, Markus ;

Stafstrom, Sven ;

Zerbetto, Francesco ;

Lazzaroni, Roberto .

NANOTECHNOLOGY, 2009, 20 (27)

[4] Diffusion, Rotation, and Surface Chemical Bond of Individual 2H-Tetraphenylporphyrin Molecules on Cu(111) [J].

Buchner, Florian ;

Xiao, Jie ;

Zillner, Elisabeth ;

Chen, Min ;

Roeckert, Michael ;

Ditze, Stefanie ;

Stark, Michael ;

Steinrueck, Hans-Peter ;

Gottfried, J. Michael ;

Marbach, Hubertus .

JOURNAL OF PHYSICAL CHEMISTRY C, 2011, 115 (49) :24172-24177

[5] Substrate-Mediated Phase Separation of Two Porphyrin Derivatives on Cu(111) [J].

Buchner, Florian ;

Zillner, Elisabeth ;

Roeckert, Michael ;

Glaessel, Stefanie ;

Steinrueck, Hans-Peter ;

Marbach, Hubertus .

CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (37) :10226-10229

[6] Ordering aspects and intramolecular conformation of tetraphenylporphyrins on Ag(111) [J].

Buchner, Florian ;

Kellner, Ina ;

Hieringer, Wolfgang ;

Goerling, Andreas ;

Steinrueck, Hans-Peter ;

Marbach, Hubertus .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2010, 12 (40) :13082-13090

[7] Exploring the bonding of large hydrocarbons on noble metals: Diindoperylene on Cu(111), Ag(111), and Au(111) [J].

Buerker, C. ;

Ferri, N. ;

Tkatchenko, A. ;

Gerlach, A. ;

Niederhausen, J. ;

Hosokai, T. ;

Duhm, S. ;

Zegenhagen, J. ;

Koch, N. ;

Schreiber, F. .

PHYSICAL REVIEW B, 2013, 87 (16)

[8] Fourier-expansion solution of atom distributions in a crystal using x-ray standing waves [J].

Cheng, L ;

Fenter, P ;

Bedzyk, MJ ;

Sturchio, NC .

PHYSICAL REVIEW LETTERS, 2003, 90 (25) :4

[9] Supramolecular Engineering through Temperature-Induced Chemical Modification of 2H-Tetraphenylporphyrin on Ag(111): Flat Phenyl Conformation and Possible Dehydrogenation Reactions [J].

Di Santo, Giovanni ;

Blankenburg, Stephan ;

Castellarin-Cudia, Carla ;

Fanetti, Mattia ;

Borghetti, Patrizia ;

Sangaletti, Luigi ;

Floreano, Luca ;

Verdini, Alberto ;

Magnano, Elena ;

Bondino, Federica ;

Pignedoli, Carlo A. ;

Manh-Thuong Nguyen ;

Gaspari, Roberto ;

Passerone, Daniele ;

Goldoni, Andrea .

CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (51) :14354-14359

[10] Investigating the molecule-substrate interaction of prototypic tetrapyrrole compounds: Adsorption and self-metalation of porphine on Cu(111) [J].

Diller, K. ;

Klappenberger, F. ;

Allegretti, F. ;

Papageorgiou, A. C. ;

Fischer, S. ;

Wiengarten, A. ;

Joshi, S. ;

Seufert, K. ;

Ecija, D. ;

Auwaerter, W. ;

Barth, J. V. .

JOURNAL OF CHEMICAL PHYSICS, 2013, 138 (15)

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