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Article: Unprecedented near-infrared (NIR) emission in diplatinum(III) (d7-d7) complexes at room temperature

TitleUnprecedented near-infrared (NIR) emission in diplatinum(III) (d7-d7) complexes at room temperature
Authors
Issue Date2010
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, 2010, v. 132 n. 20, p. 7094-7103 How to Cite?
AbstractThe synthesis and single-crystal X-ray structures of the first family of efficient NIR emitters with tunable emission energy based on dihalodiplatinum(III) (5d7-5d7) complexes of general formulae [Pt2(μ-C 6H 3-5-R-2-AsPh 2) 4X2] (R = Me or CHMe 2; X = Cl, Br or I), together with that of their diplatinum(II) (5d8-5d8) precursors ([Pt 2(μ-C 6H 3-5-R-2-AsPh2) 4]) and cyano counterparts (X = CN), are reported. The diplatinum(II) complexes with isopropyl groups are isolated initially as a mixture of two species, one being a half-lantern structure containing two bridging and two chelate C6H 3-5-CHMe2-2-AsPh2 ligands (1b) that exists in two crystalline modifications [d(Pt⋯Pt) = 3.4298(2)Å and 4.3843(2) Å]; the other is a full-lantern or paddle-wheel structure having four bridging C 6H 3-5-CHMe 2-2-AsPh 2 ligands (2b) [d(Pt⋯Pt) = 2.94795(12)Å]. Complete conversion of the isomers into 2b occurs in hot toluene. The Pt-Pt bond distances in the diplatinum(III) complexes are less than that in 2b and increase in the order X = Cl (3b) [2.6896(2) Å] < Br (4b) [2.7526(3) Å] < I (5b) [2.7927(7) Å] ∼ CN (6b) [2.7823(2), 2.7924(2) Å for two independent molecules]. Comparison with the corresponding data for our previously reported series of complexes 3a-6a (R = Me) indicates that the Pt-Pt bond lengths obtained from single-crystal X-ray analysis are influenced both by the axial ligand and by intermolecular lattice effects. Like [Pt2(μ-pop)4] 4-[pop = pyrophosphite, (P2O5H2)2-], the diplatinum(II) complexes [Pt2(μ-C6H3-5-R-2-AsPh2) 4] [R = Me (2a), CHMe2(2b)] display intense green phosphorescence, both as solids and in solution, and at room temperature and 77 K, with the emission maxima in the range 501-532 nm. In contrast to the reported dihalodiplatinum(III) complexes [Pt2(μ-pop)4X2] 4- that exhibit red luminescence only at 77 K in a glass or as a solid, complexes 3a-6a and 3b-6b are phosphorescent in the visible to near-infrared region at both room and low temperatures. The electronic spectra and photoemissive behavior are discussed on the basis of time-dependent density functional theory (TDDFT) calculations at the B3YLP level. The photoemissive states for the halide analogues 3a,b-5a,b involve a moderate to extensive mixing of XMMCT character and MC [ds-ds*] character, whereas the cyano complexes 6a and 6b are thought to involve relatively less mixing of the XMMCT character into the MC[dδ-dδ*] state. © 2010 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/168458
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorBennett, MAen_US
dc.contributor.authorBhargava, SKen_US
dc.contributor.authorCheng, ECCen_US
dc.contributor.authorLam, WHen_US
dc.contributor.authorLee, TKMen_US
dc.contributor.authorPrivér, SHen_US
dc.contributor.authorWagler, Jen_US
dc.contributor.authorWillis, ACen_US
dc.contributor.authorYam, VWWen_US
dc.date.accessioned2012-10-08T03:19:11Z-
dc.date.available2012-10-08T03:19:11Z-
dc.date.issued2010en_US
dc.identifier.citationJournal Of The American Chemical Society, 2010, v. 132 n. 20, p. 7094-7103en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://hdl.handle.net/10722/168458-
dc.description.abstractThe synthesis and single-crystal X-ray structures of the first family of efficient NIR emitters with tunable emission energy based on dihalodiplatinum(III) (5d7-5d7) complexes of general formulae [Pt2(μ-C 6H 3-5-R-2-AsPh 2) 4X2] (R = Me or CHMe 2; X = Cl, Br or I), together with that of their diplatinum(II) (5d8-5d8) precursors ([Pt 2(μ-C 6H 3-5-R-2-AsPh2) 4]) and cyano counterparts (X = CN), are reported. The diplatinum(II) complexes with isopropyl groups are isolated initially as a mixture of two species, one being a half-lantern structure containing two bridging and two chelate C6H 3-5-CHMe2-2-AsPh2 ligands (1b) that exists in two crystalline modifications [d(Pt⋯Pt) = 3.4298(2)Å and 4.3843(2) Å]; the other is a full-lantern or paddle-wheel structure having four bridging C 6H 3-5-CHMe 2-2-AsPh 2 ligands (2b) [d(Pt⋯Pt) = 2.94795(12)Å]. Complete conversion of the isomers into 2b occurs in hot toluene. The Pt-Pt bond distances in the diplatinum(III) complexes are less than that in 2b and increase in the order X = Cl (3b) [2.6896(2) Å] < Br (4b) [2.7526(3) Å] < I (5b) [2.7927(7) Å] ∼ CN (6b) [2.7823(2), 2.7924(2) Å for two independent molecules]. Comparison with the corresponding data for our previously reported series of complexes 3a-6a (R = Me) indicates that the Pt-Pt bond lengths obtained from single-crystal X-ray analysis are influenced both by the axial ligand and by intermolecular lattice effects. Like [Pt2(μ-pop)4] 4-[pop = pyrophosphite, (P2O5H2)2-], the diplatinum(II) complexes [Pt2(μ-C6H3-5-R-2-AsPh2) 4] [R = Me (2a), CHMe2(2b)] display intense green phosphorescence, both as solids and in solution, and at room temperature and 77 K, with the emission maxima in the range 501-532 nm. In contrast to the reported dihalodiplatinum(III) complexes [Pt2(μ-pop)4X2] 4- that exhibit red luminescence only at 77 K in a glass or as a solid, complexes 3a-6a and 3b-6b are phosphorescent in the visible to near-infrared region at both room and low temperatures. The electronic spectra and photoemissive behavior are discussed on the basis of time-dependent density functional theory (TDDFT) calculations at the B3YLP level. The photoemissive states for the halide analogues 3a,b-5a,b involve a moderate to extensive mixing of XMMCT character and MC [ds-ds*] character, whereas the cyano complexes 6a and 6b are thought to involve relatively less mixing of the XMMCT character into the MC[dδ-dδ*] state. © 2010 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_US
dc.relation.ispartofJournal of the American Chemical Societyen_US
dc.subject.meshCrystallography, X-Rayen_US
dc.subject.meshInfrared Raysen_US
dc.subject.meshLanthanoid Series Elements - Chemistryen_US
dc.subject.meshModels, Molecularen_US
dc.subject.meshMolecular Conformationen_US
dc.subject.meshOrganoplatinum Compounds - Chemical Synthesis - Chemistryen_US
dc.subject.meshQuantum Theoryen_US
dc.subject.meshTemperatureen_US
dc.subject.meshTransition Elements - Chemistryen_US
dc.titleUnprecedented near-infrared (NIR) emission in diplatinum(III) (d7-d7) complexes at room temperatureen_US
dc.typeArticleen_US
dc.identifier.emailLam, WH:chsue@hku.hken_US
dc.identifier.emailYam, VWW:wwyam@hku.hken_US
dc.identifier.authorityLam, WH=rp00719en_US
dc.identifier.authorityYam, VWW=rp00822en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ja1002313en_US
dc.identifier.pmid20433140-
dc.identifier.scopuseid_2-s2.0-77952575337en_US
dc.identifier.hkuros172749-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-77952575337&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume132en_US
dc.identifier.issue20en_US
dc.identifier.spage7094en_US
dc.identifier.epage7103en_US
dc.identifier.isiWOS:000277999700052-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridBennett, MA=7403467120en_US
dc.identifier.scopusauthoridBhargava, SK=7201604250en_US
dc.identifier.scopusauthoridCheng, ECC=7201743424en_US
dc.identifier.scopusauthoridLam, WH=26642862800en_US
dc.identifier.scopusauthoridLee, TKM=8610515400en_US
dc.identifier.scopusauthoridPrivér, SH=8298527200en_US
dc.identifier.scopusauthoridWagler, J=6507234109en_US
dc.identifier.scopusauthoridWillis, AC=7202176800en_US
dc.identifier.scopusauthoridYam, VWW=18539304700en_US

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