Excited States of Triphenylamine-Substituted 2-Pyridyl-1,2,3-triazole Complexes

Gregory S. Huff; Warrick K.C. Lo; Raphael Horvath; Jack O. Turner; Xue Zhong Sun; Geoffrey R. Weal; Hannah J. Davidson; Aaron D.W. Kennedy; C. John McAdam; James D. Crowley; Michael W. George; Keith C. Gordon

doi:10.1021/acs.inorgchem.6b01959

Excited States of Triphenylamine-Substituted 2-Pyridyl-1,2,3-triazole Complexes

Gregory S. Huff, Warrick K.C. Lo, Raphael Horvath, Jack O. Turner, Xue Zhong Sun, Geoffrey R. Weal, Hannah J. Davidson, Aaron D.W. Kennedy, C. John McAdam, James D. Crowley, Michael W. George, Keith C. Gordon

Department of Chemical and Environmental Engineering

Research output: Journal Publication › Article › peer-review

27 Citations (Scopus)

Abstract

A new 2-pyridyl-1,2,3-triazole (pytri) ligand, TPA-pytri, substituted with a triphenylamine (TPA) donor group on the 5 position of the pyridyl unit was synthesized and characterized. Dichloroplatinum(II), bis(phenylacetylide)platinum(II), bromotricarbonylrhenium(I), and bis(bipyridyl)ruthenium(II) complexes of this ligand were synthesized and compared to complexes of pytri ligands without the TPA substituent. The complexes of unsubstituted pytri ligands show metal-to-ligand charge-transfer (MLCT) absorption bands involving the pytri ligand in the near-UV region. These transitions are complemented by intraligand charge-transfer (ILCT) bands in the TPA-pytri complexes, resulting in greatly improved visible absorption (λ_max = 421 nm and ϵ = 19800 M^-1 cm^-1 for [Pt(TPA-pytri)Cl₂]). The resonance Raman enhancement patterns allow for assignment of these absorption bands. The [Re(TPA-pytri)(CO)₃Br] and [Pt(TPA-pytri)(CCPh)₂] complexes were examined with time-resolved infrared spectroscopy. Shifts in the CC and CO stretching bands revealed that the complexes form states with increased electron density about their metal centers. [Pt(TPA-pytri)Cl₂] is unusual in that it is emissive despite the presence of deactivating d-d states, which prevents emission from the unsubstituted pytri complex.

Original language	English
Pages (from-to)	12238-12253
Number of pages	16
Journal	Inorganic Chemistry
Volume	55
Issue number	23
DOIs	https://doi.org/10.1021/acs.inorgchem.6b01959
Publication status	Published - 5 Dec 2016

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{604ffaf731a64d4e85bebbee94c1e60d,

title = "Excited States of Triphenylamine-Substituted 2-Pyridyl-1,2,3-triazole Complexes",

abstract = "A new 2-pyridyl-1,2,3-triazole (pytri) ligand, TPA-pytri, substituted with a triphenylamine (TPA) donor group on the 5 position of the pyridyl unit was synthesized and characterized. Dichloroplatinum(II), bis(phenylacetylide)platinum(II), bromotricarbonylrhenium(I), and bis(bipyridyl)ruthenium(II) complexes of this ligand were synthesized and compared to complexes of pytri ligands without the TPA substituent. The complexes of unsubstituted pytri ligands show metal-to-ligand charge-transfer (MLCT) absorption bands involving the pytri ligand in the near-UV region. These transitions are complemented by intraligand charge-transfer (ILCT) bands in the TPA-pytri complexes, resulting in greatly improved visible absorption (λmax = 421 nm and ϵ = 19800 M-1 cm-1 for [Pt(TPA-pytri)Cl2]). The resonance Raman enhancement patterns allow for assignment of these absorption bands. The [Re(TPA-pytri)(CO)3Br] and [Pt(TPA-pytri)(CCPh)2] complexes were examined with time-resolved infrared spectroscopy. Shifts in the CC and CO stretching bands revealed that the complexes form states with increased electron density about their metal centers. [Pt(TPA-pytri)Cl2] is unusual in that it is emissive despite the presence of deactivating d-d states, which prevents emission from the unsubstituted pytri complex.",

author = "Huff, {Gregory S.} and Lo, {Warrick K.C.} and Raphael Horvath and Turner, {Jack O.} and Sun, {Xue Zhong} and Weal, {Geoffrey R.} and Davidson, {Hannah J.} and Kennedy, {Aaron D.W.} and McAdam, {C. John} and Crowley, {James D.} and George, {Michael W.} and Gordon, {Keith C.}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = dec,

day = "5",

doi = "10.1021/acs.inorgchem.6b01959",

language = "English",

volume = "55",

pages = "12238--12253",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "23",

}

TY - JOUR

T1 - Excited States of Triphenylamine-Substituted 2-Pyridyl-1,2,3-triazole Complexes

AU - Huff, Gregory S.

AU - Lo, Warrick K.C.

AU - Horvath, Raphael

AU - Turner, Jack O.

AU - Sun, Xue Zhong

AU - Weal, Geoffrey R.

AU - Davidson, Hannah J.

AU - Kennedy, Aaron D.W.

AU - McAdam, C. John

AU - Crowley, James D.

AU - George, Michael W.

AU - Gordon, Keith C.

PY - 2016/12/5

Y1 - 2016/12/5

N2 - A new 2-pyridyl-1,2,3-triazole (pytri) ligand, TPA-pytri, substituted with a triphenylamine (TPA) donor group on the 5 position of the pyridyl unit was synthesized and characterized. Dichloroplatinum(II), bis(phenylacetylide)platinum(II), bromotricarbonylrhenium(I), and bis(bipyridyl)ruthenium(II) complexes of this ligand were synthesized and compared to complexes of pytri ligands without the TPA substituent. The complexes of unsubstituted pytri ligands show metal-to-ligand charge-transfer (MLCT) absorption bands involving the pytri ligand in the near-UV region. These transitions are complemented by intraligand charge-transfer (ILCT) bands in the TPA-pytri complexes, resulting in greatly improved visible absorption (λmax = 421 nm and ϵ = 19800 M-1 cm-1 for [Pt(TPA-pytri)Cl2]). The resonance Raman enhancement patterns allow for assignment of these absorption bands. The [Re(TPA-pytri)(CO)3Br] and [Pt(TPA-pytri)(CCPh)2] complexes were examined with time-resolved infrared spectroscopy. Shifts in the CC and CO stretching bands revealed that the complexes form states with increased electron density about their metal centers. [Pt(TPA-pytri)Cl2] is unusual in that it is emissive despite the presence of deactivating d-d states, which prevents emission from the unsubstituted pytri complex.

AB - A new 2-pyridyl-1,2,3-triazole (pytri) ligand, TPA-pytri, substituted with a triphenylamine (TPA) donor group on the 5 position of the pyridyl unit was synthesized and characterized. Dichloroplatinum(II), bis(phenylacetylide)platinum(II), bromotricarbonylrhenium(I), and bis(bipyridyl)ruthenium(II) complexes of this ligand were synthesized and compared to complexes of pytri ligands without the TPA substituent. The complexes of unsubstituted pytri ligands show metal-to-ligand charge-transfer (MLCT) absorption bands involving the pytri ligand in the near-UV region. These transitions are complemented by intraligand charge-transfer (ILCT) bands in the TPA-pytri complexes, resulting in greatly improved visible absorption (λmax = 421 nm and ϵ = 19800 M-1 cm-1 for [Pt(TPA-pytri)Cl2]). The resonance Raman enhancement patterns allow for assignment of these absorption bands. The [Re(TPA-pytri)(CO)3Br] and [Pt(TPA-pytri)(CCPh)2] complexes were examined with time-resolved infrared spectroscopy. Shifts in the CC and CO stretching bands revealed that the complexes form states with increased electron density about their metal centers. [Pt(TPA-pytri)Cl2] is unusual in that it is emissive despite the presence of deactivating d-d states, which prevents emission from the unsubstituted pytri complex.

UR - http://www.scopus.com/inward/record.url?scp=85002196339&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.6b01959

DO - 10.1021/acs.inorgchem.6b01959

M3 - Article

AN - SCOPUS:85002196339

SN - 0020-1669

VL - 55

SP - 12238

EP - 12253

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 23

ER -

Excited States of Triphenylamine-Substituted 2-Pyridyl-1,2,3-triazole Complexes

Abstract

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