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Article: Homoleptic platinum(II) and palladium(II) organothiolates and phenylselenolates: Solvothermal synthesis, structural determination, optical properties, and single-source precursors for PdSe and PdS nanocrystals

TitleHomoleptic platinum(II) and palladium(II) organothiolates and phenylselenolates: Solvothermal synthesis, structural determination, optical properties, and single-source precursors for PdSe and PdS nanocrystals
Authors
KeywordsChain structures
Optical band gaps
Powder X-ray diffraction
Self-assembly formation
Solvothermal synthesis
Issue Date2010
PublisherWiley - V C H Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www.wiley-vch.de/publish/en/journals/alphabeticIndex/2451
Citation
Chemistry - An Asian Journal, 2010, v. 5 n. 9, p. 2062-2074 How to Cite?
AbstractHomoleptic d8-metal organothiolates and phenylselenolates [M-(EC 6H5)2]λ (E = S, M = Pt 1, M = Pd 2, M = Ni 5 ;E = Se, M = Pt 3, M = Pd 4) were prepared as crystalline solids under solvothermal conditions. Their structures were solved using powder X-ray diffraction data. In each case, the EC6H5 (E = S, Se) ligand binds to two metal ions (M = Pt, Pd, and Ni) to form chain-like structures with planar (in 1) or zig-zag (in 2-5) conformations. The [M(SR) 2]λ complexes (M = Pt, R = 4-tert-butylphenyl 6 ;R = 2-naphthyl 8; R= 4-nitrophenyl 10 and M = Pd, R= 4-tert-butylphenyl 7;R = 2-naphthyl 9; R= 4-nitrophenyl 11) were prepared under similar solvothermal conditions. Based on the XPS binding energies and elemental analyses, complexes 6-11 have the same [M(SR)2]λ formulation as 1 and 2. The cyclic complex [Pd6 (SCH3)12] 12 was prepared as a crystalline solid by solvothermal annealing treatment of the amorphous precipitate. A chain-like polymer structure is proposed for both [Pd(SC 12H25)2]λ 13 and [Pd(SC 16H33)2]λ 14; these polymeric chains self-assemble to give layerlike structures. Solid-state diffuse reflectance spectra reveal that the optical band gap Eg (eV) of complexes 1, 6, 8, 10 and of 2, 7, 9, 11 are in the range of 2.10-3.00 eV and 2.10-2.63 eV, respectively, and 5 has the lowest Eg value (1.72 eV). Heating solid samples of 4 and 13 under solvothermal conditions afforded phase-pure Pd 17Se15 and PdS nanocrystals, respectively. Field-effect transistors fabricated with a drop-cast thin film made from Pd 17Se15 nanocrystals prior treated with an ethanolic solution of 1-hexadecanethiol displayed ambipolar charge transporting properties with hole and electron mobility being 7 × 10-2 cm2 V-1S-1 and 6 × 10-2 cm2 V -1s-1, respectively. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Persistent Identifierhttp://hdl.handle.net/10722/124528
ISSN
2015 Impact Factor: 4.592
2015 SCImago Journal Rankings: 1.833
ISI Accession Number ID
Funding AgencyGrant Number
HKU
Strategic Research Themes on Bionanotechnology and Organic Optoelectronics
NSFC/RGCHKU 742/04
Funding Information:

The authors thank support from the University Development Fund of HKU, the Strategic Research Themes on Bionanotechnology and Organic Optoelectronics and the NSFC/RGC (HKU 742/04). The work described in this paper was partially supported by a grant from the University Grants Committee of the Hong Kong Special Administrative Region, China (Project No. [AoE/P-03/08]). SSYC thanks supports by a grant from the Seed Fund Project for Basic Research (HKU 200811159007) and acknowledges all the past and present group members of Prof. Zhengtao Xu of the City University of Hong Kong for their kind helps in collecting DRS data, Dr. Kwan-Ming Ng for his assistance in performing MALDI-MS experiment as well as Dr. Jing Ren and Professor M-H Whangbo of North Carolina State University for valuable discussions on electronic band structure calculations of the polymeric chain complexes.

References

 

DC FieldValueLanguage
dc.contributor.authorChui, SSYen_HK
dc.contributor.authorLow, KHen_HK
dc.contributor.authorLu, Jen_HK
dc.contributor.authorRoy, VALen_HK
dc.contributor.authorChan, SLFen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-10-31T10:39:34Z-
dc.date.available2010-10-31T10:39:34Z-
dc.date.issued2010en_HK
dc.identifier.citationChemistry - An Asian Journal, 2010, v. 5 n. 9, p. 2062-2074en_HK
dc.identifier.issn1861-4728en_HK
dc.identifier.urihttp://hdl.handle.net/10722/124528-
dc.description.abstractHomoleptic d8-metal organothiolates and phenylselenolates [M-(EC 6H5)2]λ (E = S, M = Pt 1, M = Pd 2, M = Ni 5 ;E = Se, M = Pt 3, M = Pd 4) were prepared as crystalline solids under solvothermal conditions. Their structures were solved using powder X-ray diffraction data. In each case, the EC6H5 (E = S, Se) ligand binds to two metal ions (M = Pt, Pd, and Ni) to form chain-like structures with planar (in 1) or zig-zag (in 2-5) conformations. The [M(SR) 2]λ complexes (M = Pt, R = 4-tert-butylphenyl 6 ;R = 2-naphthyl 8; R= 4-nitrophenyl 10 and M = Pd, R= 4-tert-butylphenyl 7;R = 2-naphthyl 9; R= 4-nitrophenyl 11) were prepared under similar solvothermal conditions. Based on the XPS binding energies and elemental analyses, complexes 6-11 have the same [M(SR)2]λ formulation as 1 and 2. The cyclic complex [Pd6 (SCH3)12] 12 was prepared as a crystalline solid by solvothermal annealing treatment of the amorphous precipitate. A chain-like polymer structure is proposed for both [Pd(SC 12H25)2]λ 13 and [Pd(SC 16H33)2]λ 14; these polymeric chains self-assemble to give layerlike structures. Solid-state diffuse reflectance spectra reveal that the optical band gap Eg (eV) of complexes 1, 6, 8, 10 and of 2, 7, 9, 11 are in the range of 2.10-3.00 eV and 2.10-2.63 eV, respectively, and 5 has the lowest Eg value (1.72 eV). Heating solid samples of 4 and 13 under solvothermal conditions afforded phase-pure Pd 17Se15 and PdS nanocrystals, respectively. Field-effect transistors fabricated with a drop-cast thin film made from Pd 17Se15 nanocrystals prior treated with an ethanolic solution of 1-hexadecanethiol displayed ambipolar charge transporting properties with hole and electron mobility being 7 × 10-2 cm2 V-1S-1 and 6 × 10-2 cm2 V -1s-1, respectively. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.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/publish/en/journals/alphabeticIndex/2451en_HK
dc.relation.ispartofChemistry - An Asian Journalen_HK
dc.subjectChain structuresen_HK
dc.subjectOptical band gapsen_HK
dc.subjectPowder X-ray diffractionen_HK
dc.subjectSelf-assembly formationen_HK
dc.subjectSolvothermal synthesisen_HK
dc.titleHomoleptic platinum(II) and palladium(II) organothiolates and phenylselenolates: Solvothermal synthesis, structural determination, optical properties, and single-source precursors for PdSe and PdS nanocrystalsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1861-4728&volume=5&issue=9&spage=2062&epage=2074&date=2010&atitle=Homoleptic+platinum(II)+and+palladium(II)+organothiolates+and+phenylselenolates:+solvothermal+synthesis,+structural+determination,+optical+properties,+and+single-source+precursors+for+PdSe+and+PdS+nanocrystals-
dc.identifier.emailChui, SSY: chuissy@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityChui, SSY=rp00686en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/asia.201000233en_HK
dc.identifier.pmid20665775-
dc.identifier.scopuseid_2-s2.0-77956454010en_HK
dc.identifier.hkuros181828en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-77956454010&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume5en_HK
dc.identifier.issue9en_HK
dc.identifier.spage2062en_HK
dc.identifier.epage2074en_HK
dc.identifier.isiWOS:000281916600016-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridChui, SSY=8297453100en_HK
dc.identifier.scopusauthoridLow, KH=7102180516en_HK
dc.identifier.scopusauthoridLu, J=36065866500en_HK
dc.identifier.scopusauthoridRoy, VAL=7005870324en_HK
dc.identifier.scopusauthoridChan, SLF=27167455400en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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