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Article: Ligand-to-ligand charge-transfer transitions of platinum(II) complexes with arylacetylide ligands with different chain lengths: Spectroscopic characterization, effect of molecular conformations, and density functional theory calculations

TitleLigand-to-ligand charge-transfer transitions of platinum(II) complexes with arylacetylide ligands with different chain lengths: Spectroscopic characterization, effect of molecular conformations, and density functional theory calculations
Authors
KeywordsDensity functional calculations
Ligand effects
Phosphorescence
Photophysics
Platinum
Uv/vis spectroscopy
Issue Date2010
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry
Citation
Chemistry - A European Journal, 2010, v. 16 n. 22, p. 6540-6554 How to Cite?
AbstractThe complexes [Pt(tBu3tpy)-{C≡C(C6H 4C≡C)n-1R}]+ (n = 1: R = alkyl and aryl (Ar); n = 1-3: R = phenyl (Ph) or Ph-N(CH3)2-4; n = 1 and 2, R = Ph-NH2-4; tBu3tpy = 4,4',4"-tri-tert-butyl-2, 2' :6',2"-terpyridine) and [Pt(Cl3tpy)(C≡CR)]+ (R = tert-butyl (tBu), Ph, 9,9'-dibutylfluorene, 9,9'-di-butyl-7-dimethyl-amine- fluorene; Cl3tpy = 4,4',4"-trichloro-2,2':6',2"-ter- pyridine) were prepared. The effects of substituent(s) on the terpyridine (tpy) and acetylide ligands and chain length of arylacetylide ligands on the absorption and emission spectra were examined. Resonance Raman (RR) spectra of [Pt(tBu3tpy)(C≡CR)]+ (R = n-butyl, Ph, and C 6H4-OCH3-4) obtained in acetonitrile at 298 K reveal that the structural distortion of the C≡C bond in the electronic excited state obtained by 502.9 nm excitation is substantially larger than that obtained by 416 nm excitation. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations on [Pt(H3tpy)-(C≡CR)] + (R= n-propyl (nPr), 2-pyr-idyl (Py)), [Pt(H3tpy) {C≡C(C6H4-C≡C)n-1Ph}]+ (n= 1-3), and [Pt(H3tpy)-{C≡C(C6H 4C≡C)n-1 C6H4-N(CH 3)2-4}]+/ +H+ (n = 1-3; H 3tpy=nonsubstituted terpyridine) at two different conformations were performed, namely, with the phenyl rings of the arylacetylide ligands coplanar ("cop") with and perpendicular ("per") to the H 3tpy ligand. Combining the experimental data and calculated results, the two lowest energy absorption peak maxima, λ1 and λ2, of [Pt(Y3tpy)(C≡CR)]+ (Y = tBu or Cl, R = aryl) are attributed to 1[π(C≡CR)→π *(Y3tpy)] in the "cop" conformation and mixed 1[dπ(Pt)-→π*-(Y3tpy]/ 1[π(C≡CR)→π*(Y3tpy)] transitions in the "per" conformation. The lowest energy absorption peak λ1 for [Pt(tBu3tPy){C≡C(C6H 4C≡C)n-1C6H4-H-4}] + (n = 1-3) shows a redshift with increasing chain length. However, for [Pt(tBu3tpy){C=C(C6H4C≡C) n-1 C6H4-N(CH3)2-4}] + (n=1-3), λ1 shows a blueshift with increasing chain length n, but shows a redshift after the addition of acid. The emissions of [Pt(Y3tpy)(C≡CR)]+ (Y=tBu or Cl) at 524-642 nm measured in dichloromethane at 298 K are assigned to the 3[π- (C≡CAr)→π*(Y3tpy)] excited states and mixed 3[dπ(Pt)→π*(Y3tpy)]/ 3[π-(C≡C)"π*(Y3tpy)] excited states for R = aryl and alkyl groups, respectively. [Pt(tBu3tpy) {C≡C(C6H4C≡C)n-1 C 6H4-N(CH3)2-4}]+ (n = 1 and 2) are nonemissive, and this is attributed to the small energy gap between the singlet ground state (S0) and the lowest triplet excited state (T1). © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Persistent Identifierhttp://hdl.handle.net/10722/134730
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
Funding AgencyGrant Number
Research Grants Council of the Hong Kong SAR, China1-IKU 7008/09
National Natural Science Foundation of China/Research Grants CouncilN HKU 752/08
Chinese Academy of Sciences/Crouchcr Foundation
University of Hong Kong
AoEprogram for the Institute of Molecular Functional Materials10208976
Funding Information:

We thank the Research Grants Council of the Hong Kong SAR, China (1-IKU 7008/09); National Natural Science Foundation of China/Research Grants Council Joint Research Scheme (N HKU 752/08), the Chinese Academy of Sciences/Crouchcr Foundation Funding Scheme for Joint Laboratories and the University Development Fund for Synthetic Chemistry of the University of Hong Kong for financial support. We are grateful to the support from the AoEprogram for the Institute of Molecular Functional Materials (10208976).

References

 

DC FieldValueLanguage
dc.contributor.authorTong, GSMen_HK
dc.contributor.authorLaw, YCen_HK
dc.contributor.authorKui, SCFen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorLeung, KHen_HK
dc.contributor.authorPhillips, DLen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2011-07-12T09:48:58Z-
dc.date.available2011-07-12T09:48:58Z-
dc.date.issued2010en_HK
dc.identifier.citationChemistry - A European Journal, 2010, v. 16 n. 22, p. 6540-6554en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/134730-
dc.description.abstractThe complexes [Pt(tBu3tpy)-{C≡C(C6H 4C≡C)n-1R}]+ (n = 1: R = alkyl and aryl (Ar); n = 1-3: R = phenyl (Ph) or Ph-N(CH3)2-4; n = 1 and 2, R = Ph-NH2-4; tBu3tpy = 4,4',4"-tri-tert-butyl-2, 2' :6',2"-terpyridine) and [Pt(Cl3tpy)(C≡CR)]+ (R = tert-butyl (tBu), Ph, 9,9'-dibutylfluorene, 9,9'-di-butyl-7-dimethyl-amine- fluorene; Cl3tpy = 4,4',4"-trichloro-2,2':6',2"-ter- pyridine) were prepared. The effects of substituent(s) on the terpyridine (tpy) and acetylide ligands and chain length of arylacetylide ligands on the absorption and emission spectra were examined. Resonance Raman (RR) spectra of [Pt(tBu3tpy)(C≡CR)]+ (R = n-butyl, Ph, and C 6H4-OCH3-4) obtained in acetonitrile at 298 K reveal that the structural distortion of the C≡C bond in the electronic excited state obtained by 502.9 nm excitation is substantially larger than that obtained by 416 nm excitation. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations on [Pt(H3tpy)-(C≡CR)] + (R= n-propyl (nPr), 2-pyr-idyl (Py)), [Pt(H3tpy) {C≡C(C6H4-C≡C)n-1Ph}]+ (n= 1-3), and [Pt(H3tpy)-{C≡C(C6H 4C≡C)n-1 C6H4-N(CH 3)2-4}]+/ +H+ (n = 1-3; H 3tpy=nonsubstituted terpyridine) at two different conformations were performed, namely, with the phenyl rings of the arylacetylide ligands coplanar ("cop") with and perpendicular ("per") to the H 3tpy ligand. Combining the experimental data and calculated results, the two lowest energy absorption peak maxima, λ1 and λ2, of [Pt(Y3tpy)(C≡CR)]+ (Y = tBu or Cl, R = aryl) are attributed to 1[π(C≡CR)→π *(Y3tpy)] in the "cop" conformation and mixed 1[dπ(Pt)-→π*-(Y3tpy]/ 1[π(C≡CR)→π*(Y3tpy)] transitions in the "per" conformation. The lowest energy absorption peak λ1 for [Pt(tBu3tPy){C≡C(C6H 4C≡C)n-1C6H4-H-4}] + (n = 1-3) shows a redshift with increasing chain length. However, for [Pt(tBu3tpy){C=C(C6H4C≡C) n-1 C6H4-N(CH3)2-4}] + (n=1-3), λ1 shows a blueshift with increasing chain length n, but shows a redshift after the addition of acid. The emissions of [Pt(Y3tpy)(C≡CR)]+ (Y=tBu or Cl) at 524-642 nm measured in dichloromethane at 298 K are assigned to the 3[π- (C≡CAr)→π*(Y3tpy)] excited states and mixed 3[dπ(Pt)→π*(Y3tpy)]/ 3[π-(C≡C)"π*(Y3tpy)] excited states for R = aryl and alkyl groups, respectively. [Pt(tBu3tpy) {C≡C(C6H4C≡C)n-1 C 6H4-N(CH3)2-4}]+ (n = 1 and 2) are nonemissive, and this is attributed to the small energy gap between the singlet ground state (S0) and the lowest triplet excited state (T1). © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.en_HK
dc.languageeng-
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistryen_HK
dc.relation.ispartofChemistry - A European Journalen_HK
dc.subjectDensity functional calculationsen_HK
dc.subjectLigand effectsen_HK
dc.subjectPhosphorescenceen_HK
dc.subjectPhotophysicsen_HK
dc.subjectPlatinumen_HK
dc.subjectUv/vis spectroscopyen_HK
dc.titleLigand-to-ligand charge-transfer transitions of platinum(II) complexes with arylacetylide ligands with different chain lengths: Spectroscopic characterization, effect of molecular conformations, and density functional theory calculationsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0947-6539&volume=16&issue=22&spage=6540&epage=6554&date=2010&atitle=Ligand-to-ligand+charge-transfer+transitions+of+platinum(II)+complexes+with+arylacetylide+ligands+with+different+chain+lengths:+spectroscopic+characterization,+effect+of+molecular+conformations,+and+density+functional+theory+calculations-
dc.identifier.emailTong, GSM: tongsm@hku.hken_HK
dc.identifier.emailKui, SCF: stevenku@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailPhillips, DL: phillips@hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityTong, GSM=rp00790en_HK
dc.identifier.authorityKui, SCF=rp00715en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.200903046en_HK
dc.identifier.pmid20422660-
dc.identifier.scopuseid_2-s2.0-77953234938en_HK
dc.identifier.hkuros172153-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-77953234938&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume16en_HK
dc.identifier.issue22en_HK
dc.identifier.spage6540en_HK
dc.identifier.epage6554en_HK
dc.identifier.isiWOS:000279445400018-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridTong, GSM=7102328656en_HK
dc.identifier.scopusauthoridLaw, YC=14042155800en_HK
dc.identifier.scopusauthoridKui, SCF=6506763660en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridLeung, KH=36139453700en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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