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Article: Unprecedented near-infrared (NIR) emission in diplatinum(III) (d7-d7) complexes at room temperature
Title | Unprecedented near-infrared (NIR) emission in diplatinum(III) (d7-d7) complexes at room temperature |
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Authors | |
Issue Date | 2010 |
Publisher | American 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? |
Abstract | The 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 Identifier | http://hdl.handle.net/10722/168458 |
ISSN | 2023 Impact Factor: 14.4 2023 SCImago Journal Rankings: 5.489 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Bennett, MA | en_US |
dc.contributor.author | Bhargava, SK | en_US |
dc.contributor.author | Cheng, ECC | en_US |
dc.contributor.author | Lam, WH | en_US |
dc.contributor.author | Lee, TKM | en_US |
dc.contributor.author | Privér, SH | en_US |
dc.contributor.author | Wagler, J | en_US |
dc.contributor.author | Willis, AC | en_US |
dc.contributor.author | Yam, VWW | en_US |
dc.date.accessioned | 2012-10-08T03:19:11Z | - |
dc.date.available | 2012-10-08T03:19:11Z | - |
dc.date.issued | 2010 | en_US |
dc.identifier.citation | Journal Of The American Chemical Society, 2010, v. 132 n. 20, p. 7094-7103 | en_US |
dc.identifier.issn | 0002-7863 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168458 | - |
dc.description.abstract | The 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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html | en_US |
dc.relation.ispartof | Journal of the American Chemical Society | en_US |
dc.subject.mesh | Crystallography, X-Ray | en_US |
dc.subject.mesh | Infrared Rays | en_US |
dc.subject.mesh | Lanthanoid Series Elements - Chemistry | en_US |
dc.subject.mesh | Models, Molecular | en_US |
dc.subject.mesh | Molecular Conformation | en_US |
dc.subject.mesh | Organoplatinum Compounds - Chemical Synthesis - Chemistry | en_US |
dc.subject.mesh | Quantum Theory | en_US |
dc.subject.mesh | Temperature | en_US |
dc.subject.mesh | Transition Elements - Chemistry | en_US |
dc.title | Unprecedented near-infrared (NIR) emission in diplatinum(III) (d7-d7) complexes at room temperature | en_US |
dc.type | Article | en_US |
dc.identifier.email | Lam, WH:chsue@hku.hk | en_US |
dc.identifier.email | Yam, VWW:wwyam@hku.hk | en_US |
dc.identifier.authority | Lam, WH=rp00719 | en_US |
dc.identifier.authority | Yam, VWW=rp00822 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ja1002313 | en_US |
dc.identifier.pmid | 20433140 | - |
dc.identifier.scopus | eid_2-s2.0-77952575337 | en_US |
dc.identifier.hkuros | 172749 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-77952575337&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 132 | en_US |
dc.identifier.issue | 20 | en_US |
dc.identifier.spage | 7094 | en_US |
dc.identifier.epage | 7103 | en_US |
dc.identifier.isi | WOS:000277999700052 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Bennett, MA=7403467120 | en_US |
dc.identifier.scopusauthorid | Bhargava, SK=7201604250 | en_US |
dc.identifier.scopusauthorid | Cheng, ECC=7201743424 | en_US |
dc.identifier.scopusauthorid | Lam, WH=26642862800 | en_US |
dc.identifier.scopusauthorid | Lee, TKM=8610515400 | en_US |
dc.identifier.scopusauthorid | Privér, SH=8298527200 | en_US |
dc.identifier.scopusauthorid | Wagler, J=6507234109 | en_US |
dc.identifier.scopusauthorid | Willis, AC=7202176800 | en_US |
dc.identifier.scopusauthorid | Yam, VWW=18539304700 | en_US |
dc.identifier.issnl | 0002-7863 | - |