Unusual Length Dependence of the Conductance in Cumulene Molecular Wires.

break junctions conductance cumulenes molecular wires single-molecule studies

Journal

Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543

Informations de publication

Date de publication:
17 Jun 2019
Historique:
received: 29 01 2019
revised: 22 04 2019
pubmed: 27 4 2019
medline: 27 4 2019
entrez: 27 4 2019
Statut: ppublish

Résumé

Cumulenes are sometimes described as "metallic" because an infinitely long cumulene would have the band structure of a metal. Herein, we report the single-molecule conductance of a series of cumulenes and cumulene analogues, where the number of consecutive C=C bonds in the core is n=1, 2, 3, and 5. The [n]cumulenes with n=3 and 5 have almost the same conductance, and they are both more conductive than the alkene (n=1). This is remarkable because molecular conductance normally falls exponentially with length. The conductance of the allene (n=2) is much lower, because of its twisted geometry. Computational simulations predict a similar trend to the experimental results and indicate that the low conductance of the allene is a general feature of [n]cumulenes where n is even. The lack of length dependence in the conductance of [3] and [5]cumulenes is attributed to the strong decrease in the HOMO-LUMO gap with increasing length.

Identifiants

pubmed: 31026371
doi: 10.1002/anie.201901228
pmc: PMC6563095
doi:

Types de publication

Journal Article

Langues

eng

Pagination

8378-8382

Subventions

Organisme : NCCIH NIH HHS
ID : F05 AT002014
Pays : United States
Organisme : Medical Research Council
ID : MR/S015329/2
Pays : United Kingdom
Organisme : Engineering and Physical Sciences Research Council
ID : EP/M016110/1, EP/M014452/1, EP/M014169/1 and EP/M029522/1
Organisme : European Research Council
ID : 320969
Pays : International

Commentaires et corrections

Type : ErratumIn

Informations de copyright

© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Références

Angew Chem Int Ed Engl. 2013 Feb 4;52(6):1817-21
pubmed: 23345193
Nano Lett. 2018 Oct 10;18(10):6387-6391
pubmed: 30187756
J Am Chem Soc. 2011 Nov 2;133(43):17160-3
pubmed: 21939263
Angew Chem Int Ed Engl. 2015 May 26;54(22):6645-9
pubmed: 25916978
Acc Chem Res. 2009 Mar 17;42(3):429-38
pubmed: 19253984
Phys Rev Lett. 2001 Aug 27;87(9):096803
pubmed: 11531588
Chem Soc Rev. 2014 May 7;43(9):3184-203
pubmed: 24671214
Phys Chem Chem Phys. 2016 Jun 1;18(22):14810-21
pubmed: 27104222
Chem Cent J. 2015 May 24;9:30
pubmed: 26029252
J Phys Condens Matter. 2008 Feb 13;20(6):064208
pubmed: 21693870
Angew Chem Int Ed Engl. 2019 Jun 17;58(25):8378-8382
pubmed: 31026371
Phys Chem Chem Phys. 2013 Oct 21;15(39):16408-25
pubmed: 24002107
Chemistry. 2015 Apr 13;21(16):6215-25
pubmed: 25765373
Acc Chem Res. 2017 Jun 20;50(6):1468-1479
pubmed: 28561581
Chem Soc Rev. 2014 Nov 7;43(21):7378-411
pubmed: 25099384
Annu Rev Phys Chem. 2001;52:681-750
pubmed: 11326078
ACS Nano. 2015 Nov 24;9(11):11109-20
pubmed: 26390251
Phys Rev Lett. 2003 Aug 15;91(7):076805
pubmed: 12935043
Nat Chem. 2010 Nov;2(11):967-71
pubmed: 20966954
Proc Natl Acad Sci U S A. 2006 Jun 6;103(23):8686-90
pubmed: 16728508
Angew Chem Int Ed Engl. 2018 Jul 2;57(27):8321-8325
pubmed: 29603858
Chem Rec. 2015 Dec;15(6):1060-74
pubmed: 26200096
J Am Chem Soc. 2018 Oct 10;140(40):12877-12883
pubmed: 30207150
Angew Chem Int Ed Engl. 2014 Apr 22;53(17):4341-5
pubmed: 24664956
J Am Chem Soc. 2005 Feb 9;127(5):1384-5
pubmed: 15686365
J Chem Phys. 2014 Mar 14;140(10):104306
pubmed: 24628168
J Am Chem Soc. 2018 Jan 17;140(2):710-718
pubmed: 29260871
J Am Chem Soc. 2013 Aug 21;135(33):12228-40
pubmed: 23875671

Auteurs

Wenjun Xu (W)

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford, OX1 3TA, UK.

Edmund Leary (E)

Department of Chemistry, Donnan and Robert Robinson Laboratories, University of Liverpool, Liverpool, L69 7ZD, UK.
Surface Science Research Centre, University of Liverpool, Oxford Street, Liverpool, L69 3BX, UK.

Songjun Hou (S)

Department of Physics, Lancaster University, Lancaster, LA1 4YW, UK.

Sara Sangtarash (S)

Department of Physics, Lancaster University, Lancaster, LA1 4YW, UK.

M Teresa González (MT)

Instituto Madrileño de Estudios Avanzados (IMDEA), Calle Faraday 9, Campus Universitario de Cantoblanco, 28049, Madrid, Spain.

Gabino Rubio-Bollinger (G)

Departamento de Física de la Materia Condensada, IFIMAC and Instituto "Nicolás Cabrera", Universidad Autónoma de Madrid, 28049, Madrid, Spain.

Qingqing Wu (Q)

Department of Physics, Lancaster University, Lancaster, LA1 4YW, UK.

Hatef Sadeghi (H)

Department of Physics, Lancaster University, Lancaster, LA1 4YW, UK.

Lara Tejerina (L)

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford, OX1 3TA, UK.

Kirsten E Christensen (KE)

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford, OX1 3TA, UK.

Nicolás Agraït (N)

Instituto Madrileño de Estudios Avanzados (IMDEA), Calle Faraday 9, Campus Universitario de Cantoblanco, 28049, Madrid, Spain.
Departamento de Física de la Materia Condensada, IFIMAC and Instituto "Nicolás Cabrera", Universidad Autónoma de Madrid, 28049, Madrid, Spain.

Simon J Higgins (SJ)

Department of Chemistry, Donnan and Robert Robinson Laboratories, University of Liverpool, Liverpool, L69 7ZD, UK.

Colin J Lambert (CJ)

Department of Physics, Lancaster University, Lancaster, LA1 4YW, UK.

Richard J Nichols (RJ)

Department of Chemistry, Donnan and Robert Robinson Laboratories, University of Liverpool, Liverpool, L69 7ZD, UK.
Surface Science Research Centre, University of Liverpool, Oxford Street, Liverpool, L69 3BX, UK.

Harry L Anderson (HL)

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford, OX1 3TA, UK.

Classifications MeSH