Flash Kinetic Spectroscopic Studies of Dinuclear Rhodium(I) Complexes

Vincent M. Miskowski; Glenn L. Nobinger; David S. Kliger; George S. Hammond; Nathan S. Lewis; Kent R. Mann; Harry B. Gray

doi:10.1021/ja00470a020

Flash Kinetic Spectroscopic Studies of Dinuclear Rhodium(I) Complexes

Vincent M. Miskowski
, Glenn L. Nobinger
, David S. Kliger
, George S. Hammond
, Nathan S. Lewis
, Kent R. Mann
, Harry B. Gray

Chemistry (Twin Cities)

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

82 Scopus citations

Abstract

Excitation of concentrated acetonitrile solutions of [Rh(tol)₄]PF₆ (tol is p-methylphenyl isocyanide) at 562 nm, where strong absorption attributable to [Rh₂(tol)_g]²⁺ occurs, produces emission (λ_max 697 nm) with a quantum yield of 0.0065 and a lifetime of ≤2 ns. Excitation of [Rh₂(bridge)₄](BPh₄)₂ (bridge is 1,3-diisocyanopropane) in acetonitrile solution at 553 nm gives emission at 656 nm with a quantum yield of 0.056 and a lifetime of ≤2 ns. The emission is assigned to ¹A_2U⇄¹A_lg (2a_1g⇄la_2u) in both dinuclear Rh(I) complexes. Excitation also gives rise to long-lived transient absorptions attributable to the following dinuclear and trinuclear species: ~8 μs, Rh₂(bridge)₄²⁺; 0.09 μs, [Rh₂(tol)₈]²⁺; and 0.14 μs, [Rh₃(tol)₁₂]³⁺. In the dinuclear complexes, this transient is most likely ³A_2u, which is the triplet excited-state partner of1A2U. The results suggest that the spin-orbit components of 3A2U possess very little singlet character.

Original language	English (US)
Pages (from-to)	485-488
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	100
Issue number	2
DOIs	https://doi.org/10.1021/ja00470a020
State	Published - 1978

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@article{a53b87cd3cdc4e028fdff6e0b5cfa0d1,

title = "Flash Kinetic Spectroscopic Studies of Dinuclear Rhodium(I) Complexes",

abstract = "Excitation of concentrated acetonitrile solutions of [Rh(tol)4]PF6 (tol is p-methylphenyl isocyanide) at 562 nm, where strong absorption attributable to [Rh2(tol)g]2+ occurs, produces emission (λmax 697 nm) with a quantum yield of 0.0065 and a lifetime of ≤2 ns. Excitation of [Rh2(bridge)4](BPh4)2 (bridge is 1,3-diisocyanopropane) in acetonitrile solution at 553 nm gives emission at 656 nm with a quantum yield of 0.056 and a lifetime of ≤2 ns. The emission is assigned to 1A2U⇄1Alg (2a1g⇄la2u) in both dinuclear Rh(I) complexes. Excitation also gives rise to long-lived transient absorptions attributable to the following dinuclear and trinuclear species: \textasciitilde{}8 μs, Rh2(bridge)42+; 0.09 μs, [Rh2(tol)8]2+; and 0.14 μs, [Rh3(tol)12]3+. In the dinuclear complexes, this transient is most likely 3A2u, which is the triplet excited-state partner of1A2U. The results suggest that the spin-orbit components of 3A2U possess very little singlet character.",

author = "Miskowski, \{Vincent M.\} and Nobinger, \{Glenn L.\} and Kliger, \{David S.\} and Hammond, \{George S.\} and Lewis, \{Nathan S.\} and Mann, \{Kent R.\} and Gray, \{Harry B.\}",

year = "1978",

doi = "10.1021/ja00470a020",

language = "English (US)",

volume = "100",

pages = "485--488",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - Flash Kinetic Spectroscopic Studies of Dinuclear Rhodium(I) Complexes

AU - Miskowski, Vincent M.

AU - Nobinger, Glenn L.

AU - Kliger, David S.

AU - Hammond, George S.

AU - Lewis, Nathan S.

AU - Mann, Kent R.

AU - Gray, Harry B.

PY - 1978

Y1 - 1978

N2 - Excitation of concentrated acetonitrile solutions of [Rh(tol)4]PF6 (tol is p-methylphenyl isocyanide) at 562 nm, where strong absorption attributable to [Rh2(tol)g]2+ occurs, produces emission (λmax 697 nm) with a quantum yield of 0.0065 and a lifetime of ≤2 ns. Excitation of [Rh2(bridge)4](BPh4)2 (bridge is 1,3-diisocyanopropane) in acetonitrile solution at 553 nm gives emission at 656 nm with a quantum yield of 0.056 and a lifetime of ≤2 ns. The emission is assigned to 1A2U⇄1Alg (2a1g⇄la2u) in both dinuclear Rh(I) complexes. Excitation also gives rise to long-lived transient absorptions attributable to the following dinuclear and trinuclear species: ~8 μs, Rh2(bridge)42+; 0.09 μs, [Rh2(tol)8]2+; and 0.14 μs, [Rh3(tol)12]3+. In the dinuclear complexes, this transient is most likely 3A2u, which is the triplet excited-state partner of1A2U. The results suggest that the spin-orbit components of 3A2U possess very little singlet character.

AB - Excitation of concentrated acetonitrile solutions of [Rh(tol)4]PF6 (tol is p-methylphenyl isocyanide) at 562 nm, where strong absorption attributable to [Rh2(tol)g]2+ occurs, produces emission (λmax 697 nm) with a quantum yield of 0.0065 and a lifetime of ≤2 ns. Excitation of [Rh2(bridge)4](BPh4)2 (bridge is 1,3-diisocyanopropane) in acetonitrile solution at 553 nm gives emission at 656 nm with a quantum yield of 0.056 and a lifetime of ≤2 ns. The emission is assigned to 1A2U⇄1Alg (2a1g⇄la2u) in both dinuclear Rh(I) complexes. Excitation also gives rise to long-lived transient absorptions attributable to the following dinuclear and trinuclear species: ~8 μs, Rh2(bridge)42+; 0.09 μs, [Rh2(tol)8]2+; and 0.14 μs, [Rh3(tol)12]3+. In the dinuclear complexes, this transient is most likely 3A2u, which is the triplet excited-state partner of1A2U. The results suggest that the spin-orbit components of 3A2U possess very little singlet character.

UR - https://www.scopus.com/pages/publications/0001256249

UR - https://www.scopus.com/pages/publications/0001256249#tab=citedBy

U2 - 10.1021/ja00470a020

DO - 10.1021/ja00470a020

M3 - Article

AN - SCOPUS:0001256249

SN - 0002-7863

VL - 100

SP - 485

EP - 488

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 2

ER -

Flash Kinetic Spectroscopic Studies of Dinuclear Rhodium(I) Complexes

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