Structural and nonlinear optical properties of aligned heterotrinuclear [RuII-(Spacer)-MII-(Spacer)-RuII] Complexes (M=Pd, Pt; spacer=4-ethynylpyridine)

Qingchun Ge; Gulliver T. Dalton; Mark G. Humphrey; Marek Samoc; T. S.Andy Hor

doi:10.1002/asia.200900065

Structural and nonlinear optical properties of aligned heterotrinuclear [Ru^II-(Spacer)-M^II-(Spacer)-Ru^II] Complexes (M=Pd, Pt; spacer=4-ethynylpyridine)

Qingchun Ge, Gulliver T. Dalton, Mark G. Humphrey, Marek Samoc, T. S.Andy Hor

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

Lewis addition between the metalloligand [RuCpACHTUNGTRENUNG(C≡Cpy-4) ACHTUNGTRENUNG(dppf)] (1) (dppf=(C₅H₄PPh₂) ₂Fe) and MCl₂ ACHTUNGTRENUNG(CH₃CN)₂ gives [RuCpACHTUNGTRENUNG(C≡Cpy-4)-ACHTUNGTRENUNG(dppf)] ₂ACHTUNGTRENUNG[MCl₂] (M=Pd (2) and Pt (3)), all of which have been spectroscopically and crystallographically characterized. The mixed-metal adducts show the d⁶-d⁸-d⁶ metal alignment maintained by the trans disposition of the directionally rigid 4-ethynylpyridine at the centrosymmetric square-planar metal center. Electrochemical studies of these and the related known complexes trans-[RuClACHTUNGTRENUNG(C≡Cpy-4)ACHTUNGTRENUNG(dppm)2] (4) and [trans-RuClACHTUNGTRENUNG(C≡Cpy-4)-ACHTUNGTRENUNG(dppm)₂] ₂ACHTUNGTRENUNG[MCl₂] (dppm=Ph₂PCH ₂PPh₂) (M=Pd (5) and Pt (6)) suggest that the spacer-linked heterotrinuclear network is able to stabilize the oxidized RuIII better than the metalloligand precursor. Cubic nonlinear optical responses are also generally higher for the heterometallic complexes. The greal value of the PdRu₂ dppm complex 5 is among the largest for linear organometallic complexes.

Original language	English
Pages (from-to)	998-1005
Number of pages	8
Journal	Chemistry - An Asian Journal
Volume	4
Issue number	6
DOIs	https://doi.org/10.1002/asia.200900065
Publication status	Published - 2 Jun 2009

Access to Document

10.1002/asia.200900065

Cite this

@article{50fdb3ac03ba44f8bcc0eed3c748c1d2,

title = "Structural and nonlinear optical properties of aligned heterotrinuclear [RuII-(Spacer)-MII-(Spacer)-RuII] Complexes (M=Pd, Pt; spacer=4-ethynylpyridine)",

abstract = "Lewis addition between the metalloligand [RuCpACHTUNGTRENUNG(C≡Cpy-4) ACHTUNGTRENUNG(dppf)] (1) (dppf=(C5H4PPh2) 2Fe) and MCl2 ACHTUNGTRENUNG(CH3CN)2 gives [RuCpACHTUNGTRENUNG(C≡Cpy-4)-ACHTUNGTRENUNG(dppf)] 2ACHTUNGTRENUNG[MCl2] (M=Pd (2) and Pt (3)), all of which have been spectroscopically and crystallographically characterized. The mixed-metal adducts show the d6-d8-d6 metal alignment maintained by the trans disposition of the directionally rigid 4-ethynylpyridine at the centrosymmetric square-planar metal center. Electrochemical studies of these and the related known complexes trans-[RuClACHTUNGTRENUNG(C≡Cpy-4)ACHTUNGTRENUNG(dppm)2] (4) and [trans-RuClACHTUNGTRENUNG(C≡Cpy-4)-ACHTUNGTRENUNG(dppm)2] 2ACHTUNGTRENUNG[MCl2] (dppm=Ph2PCH 2PPh2) (M=Pd (5) and Pt (6)) suggest that the spacer-linked heterotrinuclear network is able to stabilize the oxidized RuIII better than the metalloligand precursor. Cubic nonlinear optical responses are also generally higher for the heterometallic complexes. The greal value of the PdRu2 dppm complex 5 is among the largest for linear organometallic complexes.",

keywords = "Electrochemistry, Heterometallic, Metal-organic, Nonlinear optics",

author = "Qingchun Ge and Dalton, {Gulliver T.} and Humphrey, {Mark G.} and Marek Samoc and Hor, {T. S.Andy}",

year = "2009",

month = jun,

day = "2",

doi = "10.1002/asia.200900065",

language = "English",

volume = "4",

pages = "998--1005",

journal = "Chemistry - An Asian Journal",

issn = "1861-4728",

publisher = "John Wiley & Sons Ltd.",

number = "6",

}

TY - JOUR

T1 - Structural and nonlinear optical properties of aligned heterotrinuclear [RuII-(Spacer)-MII-(Spacer)-RuII] Complexes (M=Pd, Pt; spacer=4-ethynylpyridine)

AU - Ge, Qingchun

AU - Dalton, Gulliver T.

AU - Humphrey, Mark G.

AU - Samoc, Marek

AU - Hor, T. S.Andy

PY - 2009/6/2

Y1 - 2009/6/2

N2 - Lewis addition between the metalloligand [RuCpACHTUNGTRENUNG(C≡Cpy-4) ACHTUNGTRENUNG(dppf)] (1) (dppf=(C5H4PPh2) 2Fe) and MCl2 ACHTUNGTRENUNG(CH3CN)2 gives [RuCpACHTUNGTRENUNG(C≡Cpy-4)-ACHTUNGTRENUNG(dppf)] 2ACHTUNGTRENUNG[MCl2] (M=Pd (2) and Pt (3)), all of which have been spectroscopically and crystallographically characterized. The mixed-metal adducts show the d6-d8-d6 metal alignment maintained by the trans disposition of the directionally rigid 4-ethynylpyridine at the centrosymmetric square-planar metal center. Electrochemical studies of these and the related known complexes trans-[RuClACHTUNGTRENUNG(C≡Cpy-4)ACHTUNGTRENUNG(dppm)2] (4) and [trans-RuClACHTUNGTRENUNG(C≡Cpy-4)-ACHTUNGTRENUNG(dppm)2] 2ACHTUNGTRENUNG[MCl2] (dppm=Ph2PCH 2PPh2) (M=Pd (5) and Pt (6)) suggest that the spacer-linked heterotrinuclear network is able to stabilize the oxidized RuIII better than the metalloligand precursor. Cubic nonlinear optical responses are also generally higher for the heterometallic complexes. The greal value of the PdRu2 dppm complex 5 is among the largest for linear organometallic complexes.

AB - Lewis addition between the metalloligand [RuCpACHTUNGTRENUNG(C≡Cpy-4) ACHTUNGTRENUNG(dppf)] (1) (dppf=(C5H4PPh2) 2Fe) and MCl2 ACHTUNGTRENUNG(CH3CN)2 gives [RuCpACHTUNGTRENUNG(C≡Cpy-4)-ACHTUNGTRENUNG(dppf)] 2ACHTUNGTRENUNG[MCl2] (M=Pd (2) and Pt (3)), all of which have been spectroscopically and crystallographically characterized. The mixed-metal adducts show the d6-d8-d6 metal alignment maintained by the trans disposition of the directionally rigid 4-ethynylpyridine at the centrosymmetric square-planar metal center. Electrochemical studies of these and the related known complexes trans-[RuClACHTUNGTRENUNG(C≡Cpy-4)ACHTUNGTRENUNG(dppm)2] (4) and [trans-RuClACHTUNGTRENUNG(C≡Cpy-4)-ACHTUNGTRENUNG(dppm)2] 2ACHTUNGTRENUNG[MCl2] (dppm=Ph2PCH 2PPh2) (M=Pd (5) and Pt (6)) suggest that the spacer-linked heterotrinuclear network is able to stabilize the oxidized RuIII better than the metalloligand precursor. Cubic nonlinear optical responses are also generally higher for the heterometallic complexes. The greal value of the PdRu2 dppm complex 5 is among the largest for linear organometallic complexes.

KW - Electrochemistry

KW - Heterometallic

KW - Metal-organic

KW - Nonlinear optics

UR - http://www.scopus.com/inward/record.url?scp=67650656877&partnerID=8YFLogxK

U2 - 10.1002/asia.200900065

DO - 10.1002/asia.200900065

M3 - Article

SN - 1861-4728

VL - 4

SP - 998

EP - 1005

JO - Chemistry - An Asian Journal

JF - Chemistry - An Asian Journal

IS - 6

ER -

Structural and nonlinear optical properties of aligned heterotrinuclear [Ru^II-(Spacer)-M^II-(Spacer)-Ru^II] Complexes (M=Pd, Pt; spacer=4-ethynylpyridine)

Abstract

Access to Document

Other files and links

Fingerprint

Cite this