On‐Surface Synthesis of Ethynylene‐Bridged Anthracene Polymers

Sánchez‐Grande, Ana; Santos, José; Cirera, Borja; Lauwaet, Koen; Chutora, Taras; Edalatmanesh, Shayan; Mutombo, Pingo; Rosén, Johanna; Zbořil, Radek; Miranda, Rodolfo; Björk, Jonas; Jelı́nek, Pavel; Martı́n, Nazario; Écija, David

doi:10.1002/ange.201814154

Cited by 20 publications

(20 citation statements)

References 36 publications

(34 reference statements)

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“…Following this chemical strategy, we report the synthesis and detailed atomistic characterization by a comprehensive scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM) supported by density functional theory (DFT) study of the on-surface reactions of two distinct molecular precursors, 4BrBiA [10,10′-bis(dibromomethylene)-10 H ,10′ H -9,9′-bianthracenylidene] and 4BrAn [9,10-bis(dibromomethylene)-9,10-dihydroanthracene]. The precursors are endowed with = CBr 2 functionalities to allow homocoupling 23 , 27 . The deposition of 4BrAn and 4BrBiA on Au(111) and subsequent annealing at 500 K results in the formation of anthracene ( 1 , Fig.…”

Section: Resultsmentioning

confidence: 99%

“…1 a) and bisanthene ( 2 , Fig. 1b ) polymers, respectively 23 , 27 . Both polymers exhibit repeating moieties linked by linear bridges, but with distinct π-conjugation.…”

Section: Resultsmentioning

confidence: 99%

“…Both polymers exhibit repeating moieties linked by linear bridges, but with distinct π-conjugation. While the anthracene polymer adopts aromatic ethynylene π-conjugation character 23 , the bisanthene polymer results in the promotion of the quinoid cumulene-like character 27 .

Fig.…”

Section: Resultsmentioning

confidence: 99%

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Tailoring π-conjugation and vibrational modes to steer on-surface synthesis of pentalene-bridged ladder polymers

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The development of synthetic strategies to engineer π-conjugated polymers is of paramount importance in modern chemistry and materials science. Here we introduce a synthetic protocol based on the search for specific vibrational modes through an appropriate tailoring of the π-conjugation of the precursors, in order to increase the attempt frequency of a chemical reaction. First, we design a 1D π-conjugated polymer on Au(111), which is based on bisanthene monomers linked by cumulene bridges that tune specific vibrational modes. In a second step, upon further annealing, such vibrational modes steer the twofold cyclization reaction between adjacent bisanthene moieties, which gives rise to a long pentalene-bridged conjugated ladder polymer featuring a low bandgap. In addition, high resolution atomic force microscopy allows us to identify by atomistic insights the resonance form of the polymer, thus confirming the validity of the Glidewell and Lloyd´s rules for aromaticity. This on-surface synthetic strategy may stimulate exploiting previously precluded reactions towards π-conjugated polymers with specific structures and properties.

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Section: Resultsmentioning

confidence: 99%

“…1 a) and bisanthene ( 2 , Fig. 1b ) polymers, respectively 23 , 27 . Both polymers exhibit repeating moieties linked by linear bridges, but with distinct π-conjugation.…”

Section: Resultsmentioning

confidence: 99%

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Tailoring π-conjugation and vibrational modes to steer on-surface synthesis of pentalene-bridged ladder polymers

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“…It is a representative of π ‐conjugated hydrocarbons (linear or quasi linear), a group of molecules frequently studied by means of QC‐DMRG calculations in the C‐atom p z active space 17–19,21,23 . We have recently studied the ground state of the above mentioned defected anthracene tetramer with the QC‐DMRG method since this and similar species often appear as unwanted by‐products during on‐surface synthesis of ethynylene‐bridged anthracene polymers 66 . Depending on the defect, such species may exhibit peculiar electronic structure properties.…”

Section: Computational Detailsmentioning

confidence: 99%

Massively parallel quantum chemical density matrix renormalization group method

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We present, to the best of our knowledge, the first attempt to exploit the super‐computer platform for quantum chemical density matrix renormalization group (QC‐DMRG) calculations. We have developed the parallel scheme based on the in‐house MPI global memory library, which combines operator and symmetry sector parallelisms, and tested its performance on three different molecules, all typical candidates for QC‐DMRG calculations. In case of the largest calculation, which is the nitrogenase FeMo cofactor cluster with the active space comprising 113 electrons in 76 orbitals and bond dimension equal to 6000, our parallel approach scales up to approximately 2000 CPU cores.

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“…Pure organic 1D materials can be obtained through catalyzed CÀCcoupling reactions on surface from halogenated precursors. [7,8] Alternatively,1 D coordination-polymers (CPs) can be isolated through coordination chemistry,the covalent bond formation resulting from on-surface reactions between metal atoms and suitable linker groups. [9][10][11][12][13][14] One major advantage of this approach is the possibility to tune the properties of the wires by changing the nature of the metal and/or the ligand.…”

Section: Introductionmentioning

confidence: 99%

1D Coordination π–d Conjugated Polymers with Distinct Structures Defined by the Choice of the Transition Metal: Towards a New Class of Antiaromatic Macrocycles

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Recently p-d conjugated coordination polymers have received alot of attention owing to their unique material properties,although synthesis of long and defect-free polymers remains challenging. Herein we introduce an ovel on-surface synthesis of coordination polymers with quinoidal ligands under ultra-high vacuum conditions,whiche nables formation of flexible coordination polymers with lengths up to hundreds of nanometers.M oreover,t his procedure allows the incorporation of different transition-metal atoms with four-ortwo-fold coordination. Remarkably,t he twofold coordination mode revealed the formation of wires constituted by (electronically) independent 12-membered antiaromatic macrocycles linked together through two CÀCs ingle bonds.

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On‐Surface Synthesis of Ethynylene‐Bridged Anthracene Polymers

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.

Cited by 20 publications

References 36 publications

Tailoring π-conjugation and vibrational modes to steer on-surface synthesis of pentalene-bridged ladder polymers

Tailoring π-conjugation and vibrational modes to steer on-surface synthesis of pentalene-bridged ladder polymers

Massively parallel quantum chemical density matrix renormalization group method

1D Coordination π–d Conjugated Polymers with Distinct Structures Defined by the Choice of the Transition Metal: Towards a New Class of Antiaromatic Macrocycles

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