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Article: Homoleptic copper(I) arylthiolates as a new class of p-type charge carriers: Structures and charge mobility studies

TitleHomoleptic copper(I) arylthiolates as a new class of p-type charge carriers: Structures and charge mobility studies
Authors
KeywordsChain structures
S ligands
Semiconductors
Structure elucidation
X-ray diffraction
Issue Date2008
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry
Citation
Chemistry - A European Journal, 2008, v. 14 n. 10, p. 2965-2975 How to Cite?
AbstractPolymeric homoleptic copper(I) arylthiolates [Cu(p-SC6H 4-X)]∞ (X = CH3 (1), H (2), CH 3O (3), tBu (4), CF3 (5), NO2 (6), and COOH (7)) have been prepared as insoluble crystalline solids in good yields (75-95%). Structure determinations by powder X-ray diffraction analysis have revealed that 1-3 and 6 form polymers of infinite chain length, with the copper atoms bridged by arylthiolate ligands. Weak intra-chain π⋯π stacking interactions are present in 1-3, as evidenced by the distances (3.210 Å in 1, 3.016 Å in 2, 3.401 Å in 3) between the mean planes of neighboring phenyl rings. In the structure of 6, the intra-chain π⋯π interactions (d = 3.711 Å) are insignificant and the chain polymers are associated through weak, non-covalent C-H⋯O hydrogen-bonding interactions (d=2.586 Å). Samples of 1-7 in their polycrystalline forms proved to be thermally stable at 200-300°C; their respective decomposition temperatures are around 100°C higher than that of the aliphatic analogue [Cu(SCH3)∞. Data from in situ variable-temperature X-ray diffractometry measurements indicated that the structures of both 1 and 7 are thermally more robust than that of [Cu(SCH 3)]∞. TEM analysis revealed that the solid samples of 1-5 and [Cu(SCH3)]∞. contained homogeneously dispersed crystalline nanorods with widths of 20-250 nm, whereas smaller plate-like nanocrystals were found for 6 and 7. SAED data showed that the chain polymers of 1-3 and [Cu(SCH3)]∞ similarly extend along the long axes of their nanorods. The nanorods of 1-5 and [Cu(SCH 3)∞ have been found to exhibit p-type field-effect transistor behavior, with charge mobility (μ) values of 10 -2-10-5Cm2V-1S-1. Polycrystalline solid samples of 6 and 7 each showed a low charge mobility (< 10-6 Cm2 V-1 S-1). The charge mobility values of field-effect transistors made from crystalline nanorods of 1-3 and [Cu(SCH3)]∞ could be correlated with their unique chain-like copper-sulfur networks, with the para-substituent of the arylthiolate ligand influencing the charge-transport properties. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.
Persistent Identifierhttp://hdl.handle.net/10722/69484
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_HK
dc.contributor.authorLi, CHen_HK
dc.contributor.authorChui, SSYen_HK
dc.contributor.authorRoy, VALen_HK
dc.contributor.authorLow, KHen_HK
dc.date.accessioned2010-09-06T06:14:05Z-
dc.date.available2010-09-06T06:14:05Z-
dc.date.issued2008en_HK
dc.identifier.citationChemistry - A European Journal, 2008, v. 14 n. 10, p. 2965-2975en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69484-
dc.description.abstractPolymeric homoleptic copper(I) arylthiolates [Cu(p-SC6H 4-X)]∞ (X = CH3 (1), H (2), CH 3O (3), tBu (4), CF3 (5), NO2 (6), and COOH (7)) have been prepared as insoluble crystalline solids in good yields (75-95%). Structure determinations by powder X-ray diffraction analysis have revealed that 1-3 and 6 form polymers of infinite chain length, with the copper atoms bridged by arylthiolate ligands. Weak intra-chain π⋯π stacking interactions are present in 1-3, as evidenced by the distances (3.210 Å in 1, 3.016 Å in 2, 3.401 Å in 3) between the mean planes of neighboring phenyl rings. In the structure of 6, the intra-chain π⋯π interactions (d = 3.711 Å) are insignificant and the chain polymers are associated through weak, non-covalent C-H⋯O hydrogen-bonding interactions (d=2.586 Å). Samples of 1-7 in their polycrystalline forms proved to be thermally stable at 200-300°C; their respective decomposition temperatures are around 100°C higher than that of the aliphatic analogue [Cu(SCH3)∞. Data from in situ variable-temperature X-ray diffractometry measurements indicated that the structures of both 1 and 7 are thermally more robust than that of [Cu(SCH 3)]∞. TEM analysis revealed that the solid samples of 1-5 and [Cu(SCH3)]∞. contained homogeneously dispersed crystalline nanorods with widths of 20-250 nm, whereas smaller plate-like nanocrystals were found for 6 and 7. SAED data showed that the chain polymers of 1-3 and [Cu(SCH3)]∞ similarly extend along the long axes of their nanorods. The nanorods of 1-5 and [Cu(SCH 3)∞ have been found to exhibit p-type field-effect transistor behavior, with charge mobility (μ) values of 10 -2-10-5Cm2V-1S-1. Polycrystalline solid samples of 6 and 7 each showed a low charge mobility (< 10-6 Cm2 V-1 S-1). The charge mobility values of field-effect transistors made from crystalline nanorods of 1-3 and [Cu(SCH3)]∞ could be correlated with their unique chain-like copper-sulfur networks, with the para-substituent of the arylthiolate ligand influencing the charge-transport properties. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.en_HK
dc.languageengen_HK
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistryen_HK
dc.relation.ispartofChemistry - A European Journalen_HK
dc.subjectChain structuresen_HK
dc.subjectS ligandsen_HK
dc.subjectSemiconductorsen_HK
dc.subjectStructure elucidationen_HK
dc.subjectX-ray diffractionen_HK
dc.subject.meshCopper - chemistry-
dc.subject.meshElectric Conductivity-
dc.subject.meshOrganometallic Compounds - chemical synthesis - chemistry-
dc.subject.meshSulfhydryl Compounds - chemistry-
dc.subject.meshTransistors, Electronic-
dc.titleHomoleptic copper(I) arylthiolates as a new class of p-type charge carriers: Structures and charge mobility studiesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0947-6539&volume=14&issue=10&spage=2965&epage=2975&date=2008&atitle=Homoleptic+copper(I)+arylthiolates+as+a+new+class+of+p-type+charge+carriers:+structures+and+charge+mobility+studiesen_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.emailChui, SSY: chuissy@hkucc.hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityChui, SSY=rp00686en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.200700723en_HK
dc.identifier.pmid18350558en_HK
dc.identifier.scopuseid_2-s2.0-53849088876en_HK
dc.identifier.hkuros141826en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-53849088876&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume14en_HK
dc.identifier.issue10en_HK
dc.identifier.spage2965en_HK
dc.identifier.epage2975en_HK
dc.identifier.isiWOS:000254872600003-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridLi, CH=8731286800en_HK
dc.identifier.scopusauthoridChui, SSY=8297453100en_HK
dc.identifier.scopusauthoridRoy, VAL=7005870324en_HK
dc.identifier.scopusauthoridLow, KH=7102180516en_HK

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