Self-assembly and coverage dependent thermally induced conformational changes of Ni(<scp>ii</scp>)-meso-tetrakis (4-tert-butylphenyl) benzoporphyrin on Cu(111)

Zhang, Liang; Lepper, Michael; Stark, Michael; Lungerich, Dominik; Jux, Norbert; Hieringer, Wolfgang; Steinrück, Hans‐Peter; Marbach, Hubertus

doi:10.1039/c5cp01490e

Cited by 16 publications

(34 citation statements)

References 52 publications

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“…57 This molecule is similar to Ni-TPBP but incorporates an additional tert-butyl group at The Journal of Physical Chemistry C Article each phenyl leg, which is expected to hinder the specific intermolecular interactions between aromatic groups.…”

Section: ■ Results and Discussionmentioning

confidence: 98%

Role of Specific Intermolecular Interactions for the Arrangement of Ni(II)-5, 10, 15, 20-Tetraphenyltetrabenzoporphyrin on Cu(111)

et al. 2015

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We have studied the coverage-dependent adsorption behavior of Ni(II)-5,10,15,20-tetraphenyltetrabenzoporphyrin on Cu(111) by scanning tunneling microscopy (STM) at room temperature. At medium coverages, the molecules self-assemble into two-dimensional islands, due to mutual stabilization through intermolecular interactions. Altogether, three different supramolecular arrangements coexist at low-to-medium coverages. On the basis of highresolution STM images and density functional theory calculations, models for the three arrangements and the corresponding intramolecular conformations of the individual molecules are proposed. The observed polymorphism is attributed to a complex interplay of specific T-type and π−π stacking interactions between the phenyl groups. For Ni(II)-meso-tetrakis (4-tert-butylphenyl) benzoporphyrin, in which the aromatic periphery is modified by the attachment of tert-butyl groups, only one supramolecular arrangement on Cu(111) is found. This difference highlights the fact that the choice of peripheral ligands of the porphyrin derivatives plays an important role in the fabrication and tailoring of functional molecular architectures. Figure 5. (a) STM image of Ni-TTBPBP on Cu(111) (U bias = +1.30 V, I set = 28 pA). The superimposed models indicate a square ordering of the supramolecular arrangement and a close packing of the tert-butyl groups. (b) Schematic of Ni-TTBPBP.

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Section: ■ Results and Discussionmentioning

confidence: 98%

Role of Specific Intermolecular Interactions for the Arrangement of Ni(II)-5, 10, 15, 20-Tetraphenyltetrabenzoporphyrin on Cu(111)

et al. 2015

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“…43-45 Furthermore TPD has been used to characterize dehydrogenation rates as a function of coverage and showed that the rate of dehydrogenation is lower at higher coverages due to the stabilizing effect of higher molecular coordination. 33,34,48,49 While dehydrogenated TPPs have been studied using NEXAFS and TPD, only limited STM evidence for the nature of the product molecules exists. Röckert et al 33 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 close-packed molecular layers exhibit distinct features possibly arising from intermolecular interactions that are not present in the single-molecule regime.…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

“…26,29,35 It has been shown that altering the phenyl groups has a profound impact on the self-assembly behavior and results in deviations from the nearlysquare organization typically observed for TPPs. 19,46,[48][49][50] However the nature of the metal 3 center in TPPs adsorbed on noble metal surfaces does not typically impact self-assembly, indicating that the final geometry is primarily driven by intermolecular phenyl-phenyl interactions. 21,24,27,51 While the porphyrin core is planar in the gas phase, upon adsorption onto a metal substrate the core deforms into a saddle-like conformation that is understood as opposing pyrrole groups bending toward and away from the substrate.…”

Section: Introductionmentioning

confidence: 98%

Zinc(II) Tetraphenylporphyrin on Ag(100) and Ag(111): Multilayer Desorption and Dehydrogenation

et al. 2016

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The interaction between zinc(II) tetraphenylporphyrin (ZnTPP) molecules and the Ag(100) and Ag(111) surfaces is investigated using a combination of scanning tunneling microscopy as a local probe of the molecular adsorption configuration and x-ray, ultraviolet and inverse photoemissions as probes of the electronic structure. For each surface, a monolayer of ZnTPP, formed by multilayer desorption, exhibits a highly ordered structure in registry with the underlying surface lattice. Subsequent annealing leads to a transition from intact molecular adsorption to dehydrogenation and subsequent rehybridization. This rehybridization is both intramolecular, with a flattening of the molecules and a measurable alteration of the electronic structure, and intermolecular leading to 2D-growth of extended covalently bound structures.

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“…[1][2][3][4][5][6][7][8][9][10] Very recently,w e reported that the self-assembly of 4,4'-bis(2,6-difluoropyridin-4-yl)-1,1':4',1''-terphenyl (BDFPTP) molecules could rigorously steer the regioselectivity of the dehydrocyclization reaction and suppress defluorinated coupling because of restricted docking orientations of the BDFPTP molecules prior to commencement of the reaction. [1][2][3][4][5][6][7][8][9][10] Very recently,w e reported that the self-assembly of 4,4'-bis(2,6-difluoropyridin-4-yl)-1,1':4',1''-terphenyl (BDFPTP) molecules could rigorously steer the regioselectivity of the dehydrocyclization reaction and suppress defluorinated coupling because of restricted docking orientations of the BDFPTP molecules prior to commencement of the reaction.…”

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confidence: 99%

Steering Surface Reaction Dynamics with a Self‐Assembly Strategy: Ullmann Coupling on Metal Surfaces

et al. 2017

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Ullmann coupling of 4-bromobiphenyl thermally catalyzed on Ag(111), Cu(111), and Cu(100) surfaces was scrutinized by scanning tunneling microscopy as well as theoretical calculations. Detailed experimental evidence showed that initial formation of organometallic intermediates on the surface, as self-assembled structures or sparsely dispersed species, is determined by the subsequent reaction pathway. Specifically, the assembled organometallic intermediates at full coverage underwent a single-barrier process to directly convert into the final coupling products, while the sparsely dispersed intermediates at low coverage went through a double-barrier process via newly identified clover-shaped intermediates prior to formation of the final coupling products. These findings demonstrate that a self-assembly strategy can efficiently steer surface reaction pathways and dynamics.

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Self-assembly and coverage dependent thermally induced conformational changes of Ni(ii)-meso-tetrakis (4-tert-butylphenyl) benzoporphyrin on Cu(111)

Cited by 16 publications

References 52 publications

Role of Specific Intermolecular Interactions for the Arrangement of Ni(II)-5, 10, 15, 20-Tetraphenyltetrabenzoporphyrin on Cu(111)

Role of Specific Intermolecular Interactions for the Arrangement of Ni(II)-5, 10, 15, 20-Tetraphenyltetrabenzoporphyrin on Cu(111)

Zinc(II) Tetraphenylporphyrin on Ag(100) and Ag(111): Multilayer Desorption and Dehydrogenation

Steering Surface Reaction Dynamics with a Self‐Assembly Strategy: Ullmann Coupling on Metal Surfaces

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