Direct Imaging of Covalent Bond Structure in Single-Molecule Chemical Reactions

被引：459

作者：

de Oteyza, Dimas G. ^{[1
,2
]}

Gorman, Patrick ^{[3
]}

Chen, Yen-Chia ^{[1
,4
]}

Wickenburg, Sebastian ^{[1
,4
]}

Riss, Alexander ^{[1
]}

Mowbray, Duncan J. ^{[5
,6
,7
]}

Etkin, Grisha ^{[3
]}

Pedramrazi, Zahra ^{[1
]}

Tsai, Hsin-Zon ^{[1
]}

Rubio, Angel ^{[2
,5
,6
,7
]}

Crommie, Michael F. ^{[1
,4
]}

Fischer, Felix R. ^{[3
,4
]}

机构：

[1] Univ Calif Berkeley, Dept Phys, Berkeley, CA 94720 USA

[2] UPV EHU Mat Phys Ctr, Ctr Fis Mat CSIC, E-20018 San Sebastian, Spain

[3] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

[4] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Mat Sci Div, Berkeley, CA 94720 USA

[5] Donostia Int Phys Ctr, E-20018 San Sebastian, Spain

[6] Univ Pais Vasco UPV, EHU, Nanobio Spect Grp, E-20018 San Sebastian, Spain

[7] Univ Pais Vasco UPV, EHU, ETSF Sci Dev Ctr, Dpto Fis Mat, E-20018 San Sebastian, Spain

来源：

SCIENCE | 2013年 / 340卷 / 6139期

基金：

美国国家科学基金会; 奥地利科学基金会; 欧洲研究理事会;

关键词：

ATOMIC-FORCE MICROSCOPY; CYCLIZATION; ENEDIYNES; RESOLUTION; CATALYSIS; STEPS;

D O I：

10.1126/science.1238187

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Observing the intricate chemical transformation of an individual molecule as it undergoes a complex reaction is a long-standing challenge in molecular imaging. Advances in scanning probe microscopy now provide the tools to visualize not only the frontier orbitals of chemical reaction partners and products, but their internal covalent bond configurations as well. We used noncontact atomic force microscopy to investigate reaction-induced changes in the detailed internal bond structure of individual oligo-(phenylene-1,2-ethynylenes) on a (100) oriented silver surface as they underwent a series of cyclization processes. Our images reveal the complex surface reaction mechanisms underlying thermally induced cyclization cascades of enediynes. Calculations using ab initio density functional theory provide additional support for the proposed reaction pathways.

引用

页码：1434 / 1437

页数：4

共 26 条

[1] C1-C5 photochemical cyclization of enediynes [J].

Alabugin, IV ;

Kovalenko, SV .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (31) :9052-9053

[2] Radical-anionic cyclizations of enediynes:: Remarkable effects of benzannelation and remote substituents on cyclorearomatization reactions [J].

Alabugin, IV ;

Manoharan, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (15) :4495-4509

[3] 1,2-shifts of hydrogen atoms in aryl radicals [J].

Brooks, MA ;

Scott, LT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (23) :5444-5449

[4] Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method [J].

Enkovaara, J. ;

Rostgaard, C. ;

Mortensen, J. J. ;

Chen, J. ;

Dulak, M. ;

Ferrighi, L. ;

Gavnholt, J. ;

Glinsvad, C. ;

Haikola, V. ;

Hansen, H. A. ;

Kristoffersen, H. H. ;

Kuisma, M. ;

Larsen, A. H. ;

Lehtovaara, L. ;

Ljungberg, M. ;

Lopez-Acevedo, O. ;

Moses, P. G. ;

Ojanen, J. ;

Olsen, T. ;

Petzold, V. ;

Romero, N. A. ;

Stausholm-Moller, J. ;

Strange, M. ;

Tritsaris, G. A. ;

Vanin, M. ;

Walter, M. ;

Hammer, B. ;

Hakkinen, H. ;

Madsen, G. K. H. ;

Nieminen, R. M. ;

Norskov, J. K. ;

Puska, M. ;

Rantala, T. T. ;

Schiotz, J. ;

Thygesen, K. S. ;

Jacobsen, K. W. .

JOURNAL OF PHYSICS-CONDENSED MATTER, 2010, 22 (25)

[5] ELEMENTARY STEPS IN HETEROGENOUS CATALYSIS [J].

ERTL, G .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1990, 29 (11) :1219-1227

[6] Atomic resolution on Si(111)-(7x7) by noncontact atomic force microscopy with a force sensor based on a quartz tuning fork [J].

Giessibl, FJ .

APPLIED PHYSICS LETTERS, 2000, 76 (11) :1470-1472

[7] Advances in atomic force microscopy [J].

Giessibl, FJ .

REVIEWS OF MODERN PHYSICS, 2003, 75 (03) :949-983

[8] Bond-Order Discrimination by Atomic Force Microscopy [J].

Gross, Leo ;

Mohn, Fabian ;

Moll, Nikolaj ;

Schuler, Bruno ;

Criado, Alejandro ;

Guitian, Enrique ;

Pena, Diego ;

Gourdon, Andre ;

Meyer, Gerhard .

SCIENCE, 2012, 337 (6100) :1326-1329

[9]

Gross L, 2010, NAT CHEM, V2, P821, DOI [10.1038/NCHEM.765, 10.1038/nchem.765]

[10] The Chemical Structure of a Molecule Resolved by Atomic Force Microscopy [J].

Gross, Leo ;

Mohn, Fabian ;

Moll, Nikolaj ;

Liljeroth, Peter ;

Meyer, Gerhard .

SCIENCE, 2009, 325 (5944) :1110-1114

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