Antiaromatic bisindeno-[n]thienoacenes with small singlet biradical characters: Syntheses, structures and chain length dependent physical properties

Handle URI:
http://hdl.handle.net/10754/563242
Title:
Antiaromatic bisindeno-[n]thienoacenes with small singlet biradical characters: Syntheses, structures and chain length dependent physical properties
Authors:
Shi, Xueliang; Burrezo, Paula Mayorga; Lee, Sangsu; Zhang, Wenhua; Zheng, Bin; Dai, Gaole; Chang, Jingjing; Lõpez Navarrete, Juan Teodomiro; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Kim, Dongho; Casado, Juan; Chi, Chunyan
Abstract:
Recent studies demonstrated that aromaticity and biradical character play important roles in determining the ground-state structures and physical properties of quinoidal polycyclic hydrocarbons and oligothiophenes, a kind of molecular materials showing promising applications for organic electronics, photonics and spintronics. In this work, we designed and synthesized a new type of hybrid system, the so-called bisindeno-[n]thienoacenes (n = 1-4), by annulation of quinoidal fused α-oligothiophenes with two indene units. The obtained molecules can be regarded as antiaromatic systems containing 4n π electrons with small singlet biradical character (y0). Their ground-state geometry and electronic structures were studied by X-ray crystallographic analysis, NMR, ESR and Raman spectroscopy, assisted by density functional theory calculations. With extension of the chain length, the molecules showed a gradual increase of the singlet biradical character accompanied by decreased antiaromaticity, finally leading to a highly reactive bisindeno[4]thienoacene (S4-TIPS) which has a singlet biradical ground state (y0= 0.202). Their optical and electronic properties in the neutral and charged states were systematically investigated by one-photon absorption, two-photon absorption, transient absorption spectroscopy, cyclic voltammetry and spectroelectrochemistry, which could be correlated to the chain length dependent antiaromaticity and biradical character. Our detailed studies revealed a clear structure-aromaticity-biradical character-physical properties-reactivity relationship, which is of importance for tailored material design in the future. This journal is
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program; HCL
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Chem. Sci.
Issue Date:
2014
DOI:
10.1039/c4sc01769b
Type:
Article
ISSN:
20416520
Sponsors:
C.C. acknowledges financial support from MOE AcRF Tier 1 grants (R-143-000-510-112 and R-143-000-573-112) and NUS Start Up grant R-143-000-486-133. The work at the University of Malaga was supported by MINECO of Spain (CTQ2012-33733) and by the Junta de Andalucia (Project P09-FQM-4708). The work at Yonsei Univ. was supported by the Mid-career Researcher Program (2010-0029668) and the Global Research Laboratory (2013K1A1A2A02050183) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT (Information and Communication Technologies) and Future Planning. K. H. acknowledges financial support from KAUST. During the reviewing process of this manuscript, a paper on a similar system was published as a Just Accepted article.<SUP>32</SUP>
Is Supplemented By:
Shi, X., Burrezo, P. M., Lee, S., Zhang, W., Zheng, B., Dai, G., … Chi, C. (2014). CCDC 1004903: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12qp7q; DOI:10.5517/cc12qp7q; HANDLE:http://hdl.handle.net/10754/624322; Shi, X., Burrezo, P. M., Lee, S., Zhang, W., Zheng, B., Dai, G., … Chi, C. (2014). CCDC 1004904: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12qp8r; DOI:10.5517/cc12qp8r; HANDLE:http://hdl.handle.net/10754/624323; Shi, X., Burrezo, P. M., Lee, S., Zhang, W., Zheng, B., Dai, G., … Chi, C. (2014). CCDC 1004905: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12qp9s; DOI:10.5517/cc12qp9s; HANDLE:http://hdl.handle.net/10754/624324; Shi, X., Burrezo, P. M., Lee, S., Zhang, W., Zheng, B., Dai, G., … Chi, C. (2014). CCDC 1004906: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12qpbt; DOI:10.5517/cc12qpbt; HANDLE:http://hdl.handle.net/10754/624325; Shi, X., Burrezo, P. M., Lee, S., Zhang, W., Zheng, B., Dai, G., … Chi, C. (2014). CCDC 1004907: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12qpcv; DOI:10.5517/cc12qpcv; HANDLE:http://hdl.handle.net/10754/624326
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorShi, Xueliangen
dc.contributor.authorBurrezo, Paula Mayorgaen
dc.contributor.authorLee, Sangsuen
dc.contributor.authorZhang, Wenhuaen
dc.contributor.authorZheng, Binen
dc.contributor.authorDai, Gaoleen
dc.contributor.authorChang, Jingjingen
dc.contributor.authorLõpez Navarrete, Juan Teodomiroen
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorKim, Donghoen
dc.contributor.authorCasado, Juanen
dc.contributor.authorChi, Chunyanen
dc.date.accessioned2015-08-03T11:43:56Zen
dc.date.available2015-08-03T11:43:56Zen
dc.date.issued2014en
dc.identifier.issn20416520en
dc.identifier.doi10.1039/c4sc01769ben
dc.identifier.urihttp://hdl.handle.net/10754/563242en
dc.description.abstractRecent studies demonstrated that aromaticity and biradical character play important roles in determining the ground-state structures and physical properties of quinoidal polycyclic hydrocarbons and oligothiophenes, a kind of molecular materials showing promising applications for organic electronics, photonics and spintronics. In this work, we designed and synthesized a new type of hybrid system, the so-called bisindeno-[n]thienoacenes (n = 1-4), by annulation of quinoidal fused α-oligothiophenes with two indene units. The obtained molecules can be regarded as antiaromatic systems containing 4n π electrons with small singlet biradical character (y0). Their ground-state geometry and electronic structures were studied by X-ray crystallographic analysis, NMR, ESR and Raman spectroscopy, assisted by density functional theory calculations. With extension of the chain length, the molecules showed a gradual increase of the singlet biradical character accompanied by decreased antiaromaticity, finally leading to a highly reactive bisindeno[4]thienoacene (S4-TIPS) which has a singlet biradical ground state (y0= 0.202). Their optical and electronic properties in the neutral and charged states were systematically investigated by one-photon absorption, two-photon absorption, transient absorption spectroscopy, cyclic voltammetry and spectroelectrochemistry, which could be correlated to the chain length dependent antiaromaticity and biradical character. Our detailed studies revealed a clear structure-aromaticity-biradical character-physical properties-reactivity relationship, which is of importance for tailored material design in the future. This journal isen
dc.description.sponsorshipC.C. acknowledges financial support from MOE AcRF Tier 1 grants (R-143-000-510-112 and R-143-000-573-112) and NUS Start Up grant R-143-000-486-133. The work at the University of Malaga was supported by MINECO of Spain (CTQ2012-33733) and by the Junta de Andalucia (Project P09-FQM-4708). The work at Yonsei Univ. was supported by the Mid-career Researcher Program (2010-0029668) and the Global Research Laboratory (2013K1A1A2A02050183) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT (Information and Communication Technologies) and Future Planning. K. H. acknowledges financial support from KAUST. During the reviewing process of this manuscript, a paper on a similar system was published as a Just Accepted article.<SUP>32</SUP>en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.titleAntiaromatic bisindeno-[n]thienoacenes with small singlet biradical characters: Syntheses, structures and chain length dependent physical propertiesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentHCLen
dc.identifier.journalChem. Sci.en
dc.contributor.institutionDepartment of Chemistry, National University of Singapore, 3 Science Drive 3Singapore, Singaporeen
dc.contributor.institutionDepartment of Physical Chemistry, University of Malaga, Campus de Teatinos s/nMalaga, Spainen
dc.contributor.institutionDepartment of Chemistry, Yonsei UniversitySeoul, South Koreaen
dc.contributor.institutionInstitute of Materials Research and Engineering, ASTAR 3 Research LinkSingapore, Singaporeen
kaust.authorZheng, Binen
kaust.authorHuang, Kuo-Weien
dc.relation.isSupplementedByShi, X., Burrezo, P. M., Lee, S., Zhang, W., Zheng, B., Dai, G., … Chi, C. (2014). CCDC 1004903: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12qp7qen
dc.relation.isSupplementedByDOI:10.5517/cc12qp7qen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624322en
dc.relation.isSupplementedByShi, X., Burrezo, P. M., Lee, S., Zhang, W., Zheng, B., Dai, G., … Chi, C. (2014). CCDC 1004904: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12qp8ren
dc.relation.isSupplementedByDOI:10.5517/cc12qp8ren
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624323en
dc.relation.isSupplementedByShi, X., Burrezo, P. M., Lee, S., Zhang, W., Zheng, B., Dai, G., … Chi, C. (2014). CCDC 1004905: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12qp9sen
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dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624324en
dc.relation.isSupplementedByShi, X., Burrezo, P. M., Lee, S., Zhang, W., Zheng, B., Dai, G., … Chi, C. (2014). CCDC 1004906: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12qpbten
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dc.relation.isSupplementedByShi, X., Burrezo, P. M., Lee, S., Zhang, W., Zheng, B., Dai, G., … Chi, C. (2014). CCDC 1004907: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc12qpcven
dc.relation.isSupplementedByDOI:10.5517/cc12qpcven
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624326en
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