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Article: Polymorphic Forms of a Gold(I) Arylacetylide Complex with Contrasting Phosphorescent Characteristics

TitlePolymorphic Forms of a Gold(I) Arylacetylide Complex with Contrasting Phosphorescent Characteristics
Authors
Issue Date2003
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 2003, v. 125 n. 51, p. 16081-16088 How to Cite?
AbstractThe spectroscopic properties and crystal structures of the gold(I) arylacetylide complexes [(R 3P)-Au(C≡CAr)] (R = Cy, Ar = 4-nitrophenyl, 1; 4-trifluoromethylphenyl, 2; pentafluorophenyl, 3; R = Ph, Ar = 4-nitrophenyl, 4) have been examined. The dipole-allowed and -forbidden transitions of 1 (4 in parentheses) at λ max 340 (336) and ca. 485 (470) nm in CH 2Cl 2 solution at 298 K are assigned to the singlet and triplet intraligand charge transfer (ILCT) transitions of the 4-nitrophenylacetylide moiety, whereas 2 (3 in parentheses) shows localized singlet and triplet acetylenic ππ* transitions at λ max 287 (276) and 426 nm, respectively. Two polymorphs of 1 with contrasting phosphorescent characteristics have been identified. At 298 K, the emissive form of 1, as well as 2-4, are highly phosphorescent with peak maximum at 504, 425, 521, and 495 nm, respectively; the other polymorph of 1 is nonemissive at 298 K but emission is detected at 77 K with peak maximum at 486 nm. Crystallographic studies reveal that the major differences between the emissive and nonemissive forms of 1 are the orientations of the molecular dipoles and the dihedral angles between neighboring 4-nitrophenyl moieties. Crystal 2 is isostructural to the nonemissive form of 1, but does not display polymorphism. The molecular planes of two neighboring lumophores are coplanar in the emissive form of 1, parallel in 4, and nearly perpendicular (78.6°) to each other in the nonemissive form of 1. Both the nature of the excited state and the dihedral angle between adjacent [Au(C≡CAr)] moieties determine the phosphorescent properties of these molecular crystals.
Persistent Identifierhttp://hdl.handle.net/10722/68809
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLu, Wen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:07:55Z-
dc.date.available2010-09-06T06:07:55Z-
dc.date.issued2003en_HK
dc.identifier.citationJournal Of The American Chemical Society, 2003, v. 125 n. 51, p. 16081-16088en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/68809-
dc.description.abstractThe spectroscopic properties and crystal structures of the gold(I) arylacetylide complexes [(R 3P)-Au(C≡CAr)] (R = Cy, Ar = 4-nitrophenyl, 1; 4-trifluoromethylphenyl, 2; pentafluorophenyl, 3; R = Ph, Ar = 4-nitrophenyl, 4) have been examined. The dipole-allowed and -forbidden transitions of 1 (4 in parentheses) at λ max 340 (336) and ca. 485 (470) nm in CH 2Cl 2 solution at 298 K are assigned to the singlet and triplet intraligand charge transfer (ILCT) transitions of the 4-nitrophenylacetylide moiety, whereas 2 (3 in parentheses) shows localized singlet and triplet acetylenic ππ* transitions at λ max 287 (276) and 426 nm, respectively. Two polymorphs of 1 with contrasting phosphorescent characteristics have been identified. At 298 K, the emissive form of 1, as well as 2-4, are highly phosphorescent with peak maximum at 504, 425, 521, and 495 nm, respectively; the other polymorph of 1 is nonemissive at 298 K but emission is detected at 77 K with peak maximum at 486 nm. Crystallographic studies reveal that the major differences between the emissive and nonemissive forms of 1 are the orientations of the molecular dipoles and the dihedral angles between neighboring 4-nitrophenyl moieties. Crystal 2 is isostructural to the nonemissive form of 1, but does not display polymorphism. The molecular planes of two neighboring lumophores are coplanar in the emissive form of 1, parallel in 4, and nearly perpendicular (78.6°) to each other in the nonemissive form of 1. Both the nature of the excited state and the dihedral angle between adjacent [Au(C≡CAr)] moieties determine the phosphorescent properties of these molecular crystals.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_HK
dc.relation.ispartofJournal of the American Chemical Societyen_HK
dc.titlePolymorphic Forms of a Gold(I) Arylacetylide Complex with Contrasting Phosphorescent Characteristicsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0002-7863&volume=125&spage=16081&epage=16088&date=2003&atitle=Polymorphic+forms+of+a+gold(I)+arylacetylide+complex+with+contrasting+phosphorescent+characteristicsen_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja0382415en_HK
dc.identifier.scopuseid_2-s2.0-0346994907en_HK
dc.identifier.hkuros91150en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0346994907&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume125en_HK
dc.identifier.issue51en_HK
dc.identifier.spage16081en_HK
dc.identifier.epage16088en_HK
dc.identifier.isiWOS:000187436200075-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLu, W=55277832700en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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