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Article: π-π interactions in organometallic systems. Crystal structures and spectroscopic properties of luminescent mono-, bi-, and trinuclear trans-cyclometalated platinum(II) complexes derived from 2,6-diphenylpyridine
Title | π-π interactions in organometallic systems. Crystal structures and spectroscopic properties of luminescent mono-, bi-, and trinuclear trans-cyclometalated platinum(II) complexes derived from 2,6-diphenylpyridine |
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Authors | |
Issue Date | 2001 |
Publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics |
Citation | Organometallics, 2001, v. 20 n. 12, p. 2477-2486 How to Cite? |
Abstract | A series of mono- and multinuclear dicyclometalated platinum(II) complexes, namely, [Pt-(C NC)L 1] [HC NCH = 2,6-diphenylpyridine; L 1 = 4-tert-butylpyridine (1), 1-methyl-4,4′-bipyridinium (MQ +) hexafluorophosphate (2(PF 6)), 2,6-dimethylphenylisocyanide (4), tricyclohexylphosphine (5), triphenylphosphine (7)], [Pt 2(C NC) 2(μ-L 2)] [L 2 = pyrazine (pyr; 3), bis(dicyclohexylphosphino)methane (dcpm; 6), bis(diphenylphosphino)methane (dppm; 8)], and [Pt 3(C NC) 3(μ 3-dpmp)] [dpmp = bis(diphenylphosphinomethyl)phenylphosphine (9)], were synthesized from [Pt(C NC)dmso] (dmso = dimethyl sulfoxide). The X-ray crystal structures of 1,3·CHCl 3, 4, 6·CHCl 3·CH 3OH·4H 2O, 7, 8 (yellow form), and 8·CHCl 3 (orange form) have been determined. For complex 1, the Pt(C NC) units are oriented into pairs in a head-to-tail fashion with an interplanar separation of 3.40 Å. For complex 4, dimeric π-π overlap between Pt(C NC) and phenyl moieties in a head-to-tail manner is observed, with interplanar stacking at 3.39 Å. There are two crystal forms for complex 8. Only one intramolecular Pt(C NC)-phenyl π-π interaction (separation 3.381 Å) is apparent in the yellow form. For the orange form (8·CHCl 3), there are two intramolecular Pt(C NC)-phenyl π-π contacts (separations 3.115 and 3.287 Å). For 3·CHCl 3, the dihedral angles between the pyrazine and the two Pt(C NC) planes are 124.0° and 130.5°, which allows the possibility for partial orbital interaction between the (5d)Pt and pπ*(pyrazine) orbitals. Complexes 1 and 4-9 display vibronically structured emission (λ max of most intense band = 508-526 nm) in 77 K methanol/ethanol (1:5, v/v) glass, which are assigned to 3IL excited states. For 1, 4-6, 8, and 9, the 77 K structureless emission at λ max 596-636 nm in methanol/ethanol glasses is assigned as ππ* excimeric in nature. These excimeric emissions are concentration-dependent for 1 and 4-6 and concentration-independent for 8 and 9. The 298 K solid emission spectra of 1, 4-6, 8, and 9 are characterized by a broad, unstructured band at λ max 566-633 nm, which red-shift in energy upon cooling to 77 K. These bands are comparable in energy to the 77 K glassy emissions and are similarly assigned. Complexes 2 and 3 show an intense absorption at λ max 410 (shoulder) and 456 nm, which are ascribed to the MLCT (5d)Pt → π*(1-methyl-4,4′-bipyridinium/pyrazine) transition, respectively. Likewise, the solid-state emissions of 2 and 3 at λ max 686 and 658 nm, respectively, are assigned as MLCT. The vapochromism of complex 8 has been investigated. |
Persistent Identifier | http://hdl.handle.net/10722/167704 |
ISSN | 2023 Impact Factor: 2.5 2023 SCImago Journal Rankings: 0.654 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Lu, W | en_US |
dc.contributor.author | Chan, MCW | en_US |
dc.contributor.author | Cheung, KK | en_US |
dc.contributor.author | Che, CM | en_US |
dc.date.accessioned | 2012-10-08T03:10:14Z | - |
dc.date.available | 2012-10-08T03:10:14Z | - |
dc.date.issued | 2001 | en_US |
dc.identifier.citation | Organometallics, 2001, v. 20 n. 12, p. 2477-2486 | en_US |
dc.identifier.issn | 0276-7333 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167704 | - |
dc.description.abstract | A series of mono- and multinuclear dicyclometalated platinum(II) complexes, namely, [Pt-(C NC)L 1] [HC NCH = 2,6-diphenylpyridine; L 1 = 4-tert-butylpyridine (1), 1-methyl-4,4′-bipyridinium (MQ +) hexafluorophosphate (2(PF 6)), 2,6-dimethylphenylisocyanide (4), tricyclohexylphosphine (5), triphenylphosphine (7)], [Pt 2(C NC) 2(μ-L 2)] [L 2 = pyrazine (pyr; 3), bis(dicyclohexylphosphino)methane (dcpm; 6), bis(diphenylphosphino)methane (dppm; 8)], and [Pt 3(C NC) 3(μ 3-dpmp)] [dpmp = bis(diphenylphosphinomethyl)phenylphosphine (9)], were synthesized from [Pt(C NC)dmso] (dmso = dimethyl sulfoxide). The X-ray crystal structures of 1,3·CHCl 3, 4, 6·CHCl 3·CH 3OH·4H 2O, 7, 8 (yellow form), and 8·CHCl 3 (orange form) have been determined. For complex 1, the Pt(C NC) units are oriented into pairs in a head-to-tail fashion with an interplanar separation of 3.40 Å. For complex 4, dimeric π-π overlap between Pt(C NC) and phenyl moieties in a head-to-tail manner is observed, with interplanar stacking at 3.39 Å. There are two crystal forms for complex 8. Only one intramolecular Pt(C NC)-phenyl π-π interaction (separation 3.381 Å) is apparent in the yellow form. For the orange form (8·CHCl 3), there are two intramolecular Pt(C NC)-phenyl π-π contacts (separations 3.115 and 3.287 Å). For 3·CHCl 3, the dihedral angles between the pyrazine and the two Pt(C NC) planes are 124.0° and 130.5°, which allows the possibility for partial orbital interaction between the (5d)Pt and pπ*(pyrazine) orbitals. Complexes 1 and 4-9 display vibronically structured emission (λ max of most intense band = 508-526 nm) in 77 K methanol/ethanol (1:5, v/v) glass, which are assigned to 3IL excited states. For 1, 4-6, 8, and 9, the 77 K structureless emission at λ max 596-636 nm in methanol/ethanol glasses is assigned as ππ* excimeric in nature. These excimeric emissions are concentration-dependent for 1 and 4-6 and concentration-independent for 8 and 9. The 298 K solid emission spectra of 1, 4-6, 8, and 9 are characterized by a broad, unstructured band at λ max 566-633 nm, which red-shift in energy upon cooling to 77 K. These bands are comparable in energy to the 77 K glassy emissions and are similarly assigned. Complexes 2 and 3 show an intense absorption at λ max 410 (shoulder) and 456 nm, which are ascribed to the MLCT (5d)Pt → π*(1-methyl-4,4′-bipyridinium/pyrazine) transition, respectively. Likewise, the solid-state emissions of 2 and 3 at λ max 686 and 658 nm, respectively, are assigned as MLCT. The vapochromism of complex 8 has been investigated. | en_US |
dc.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics | en_US |
dc.relation.ispartof | Organometallics | en_US |
dc.title | π-π interactions in organometallic systems. Crystal structures and spectroscopic properties of luminescent mono-, bi-, and trinuclear trans-cyclometalated platinum(II) complexes derived from 2,6-diphenylpyridine | en_US |
dc.type | Article | en_US |
dc.identifier.email | Lu, W:luwei@hku.hk | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Lu, W=rp00754 | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/om0009839 | en_US |
dc.identifier.scopus | eid_2-s2.0-0035844918 | en_US |
dc.identifier.hkuros | 62463 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-0035844918&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 20 | en_US |
dc.identifier.issue | 12 | en_US |
dc.identifier.spage | 2477 | en_US |
dc.identifier.epage | 2486 | en_US |
dc.identifier.isi | WOS:000169242700014 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Lu, W=27868087600 | en_US |
dc.identifier.scopusauthorid | Chan, MCW=7402598116 | en_US |
dc.identifier.scopusauthorid | Cheung, KK=7402406613 | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.issnl | 0276-7333 | - |