Bis(4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine) ruthenium(ii) complexes and their N-alkylated derivatives in catalytic light-driven water oxidation

Hongjin Lv; Jennifer A. Rudd; Petro F. Zhuk; Ji Young Lee; Edwin C. Constable; Catherine E. Housecroft; Craig L. Hill; Djamaladdin G. Musaev; Yurii V. Geletii

doi:10.1039/c3ra44192j

Bis(4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine) ruthenium(ii) complexes and their N-alkylated derivatives in catalytic light-driven water oxidation

Hongjin Lv, Jennifer A. Rudd, Petro F. Zhuk, Ji Young Lee, Edwin C. Constable, Catherine E. Housecroft^*, Craig L. Hill, Djamaladdin G. Musaev, Yurii V. Geletii

^*Corresponding author for this work

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

19 Citations (Scopus)

Abstract

Hydrogen sulfate salts of [Ru(1)₂]²⁺ where 1 = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine and four N-alkylated derivatives [Ru(L)₂]⁴⁺ were used as photosensitizers (λ_max ∼510 nm) for water oxidation in light driven reactions with peroxydisulfate as a sacrificial electron acceptor and Na₁₀[Co₄(H₂O)₂(α-PW ₉O₃₄)₂] (Co₄POM) as the catalyst in sodium borate buffers at pH 8.0 and 9.0. The N-substituents investigated were benzyl (L⁺ = 2⁺), ethyl (L⁺ = 3⁺), allyl (L⁺ = 4⁺) and 4-cyanobenzyl (L⁺ = 5 ⁺). The O₂ yield in the presence of [Ru(L) ₂]⁴⁺ (L⁺ = 2⁺-4⁺) was comparable to that obtained in the presence [Ru(bpy)₃]²⁺ (bpy = 2,2′-bipyridine) using light sources with λ_max ≈ 490 nm. The ruthenium(iii) complexes [Ru(1)₂]³⁺ and [Ru(L)₂]⁵⁺ (L⁺ = 2⁺-5⁺) are rather unstable in acidic conditions and could not be isolated. The most efficient photosensitizers [Ru(L)₂]⁵⁺ (L⁺ = 2⁺ and 4⁺) were the least stable under weakly basic conditions (pH 9.0) with a half-life τ_1/2 ∼ 10 ms. The stability of the complexes under photocatalytic turnover conditions is probably controlled by the rate at which ligand L⁺ is oxidized by Co ₄POM in its highest oxidation state.

Original language	English
Pages (from-to)	20647-20654
Number of pages	8
Journal	RSC Advances
Volume	3
Issue number	43
DOIs	https://doi.org/10.1039/c3ra44192j
Publication status	Published - 21 Nov 2013
Externally published	Yes

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@article{a6a2392393ee427e971a6e6e6e1be0f2,

title = "Bis(4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine) ruthenium(ii) complexes and their N-alkylated derivatives in catalytic light-driven water oxidation",

abstract = "Hydrogen sulfate salts of [Ru(1)2]2+ where 1 = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine and four N-alkylated derivatives [Ru(L)2]4+ were used as photosensitizers (λmax ∼510 nm) for water oxidation in light driven reactions with peroxydisulfate as a sacrificial electron acceptor and Na10[Co4(H2O)2(α-PW 9O34)2] (Co4POM) as the catalyst in sodium borate buffers at pH 8.0 and 9.0. The N-substituents investigated were benzyl (L+ = 2+), ethyl (L+ = 3+), allyl (L+ = 4+) and 4-cyanobenzyl (L+ = 5 +). The O2 yield in the presence of [Ru(L) 2]4+ (L+ = 2+-4+) was comparable to that obtained in the presence [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) using light sources with λmax ≈ 490 nm. The ruthenium(iii) complexes [Ru(1)2]3+ and [Ru(L)2]5+ (L+ = 2+-5+) are rather unstable in acidic conditions and could not be isolated. The most efficient photosensitizers [Ru(L)2]5+ (L+ = 2+ and 4+) were the least stable under weakly basic conditions (pH 9.0) with a half-life τ1/2 ∼ 10 ms. The stability of the complexes under photocatalytic turnover conditions is probably controlled by the rate at which ligand L+ is oxidized by Co 4POM in its highest oxidation state.",

author = "Hongjin Lv and Rudd, {Jennifer A.} and Zhuk, {Petro F.} and Lee, {Ji Young} and Constable, {Edwin C.} and Housecroft, {Catherine E.} and Hill, {Craig L.} and Musaev, {Djamaladdin G.} and Geletii, {Yurii V.}",

year = "2013",

month = nov,

day = "21",

doi = "10.1039/c3ra44192j",

language = "English",

volume = "3",

pages = "20647--20654",

journal = "RSC Advances",

issn = "2046-2069",

publisher = "Royal Society of Chemistry",

number = "43",

}

TY - JOUR

T1 - Bis(4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine) ruthenium(ii) complexes and their N-alkylated derivatives in catalytic light-driven water oxidation

AU - Lv, Hongjin

AU - Rudd, Jennifer A.

AU - Zhuk, Petro F.

AU - Lee, Ji Young

AU - Constable, Edwin C.

AU - Housecroft, Catherine E.

AU - Hill, Craig L.

AU - Musaev, Djamaladdin G.

AU - Geletii, Yurii V.

PY - 2013/11/21

Y1 - 2013/11/21

N2 - Hydrogen sulfate salts of [Ru(1)2]2+ where 1 = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine and four N-alkylated derivatives [Ru(L)2]4+ were used as photosensitizers (λmax ∼510 nm) for water oxidation in light driven reactions with peroxydisulfate as a sacrificial electron acceptor and Na10[Co4(H2O)2(α-PW 9O34)2] (Co4POM) as the catalyst in sodium borate buffers at pH 8.0 and 9.0. The N-substituents investigated were benzyl (L+ = 2+), ethyl (L+ = 3+), allyl (L+ = 4+) and 4-cyanobenzyl (L+ = 5 +). The O2 yield in the presence of [Ru(L) 2]4+ (L+ = 2+-4+) was comparable to that obtained in the presence [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) using light sources with λmax ≈ 490 nm. The ruthenium(iii) complexes [Ru(1)2]3+ and [Ru(L)2]5+ (L+ = 2+-5+) are rather unstable in acidic conditions and could not be isolated. The most efficient photosensitizers [Ru(L)2]5+ (L+ = 2+ and 4+) were the least stable under weakly basic conditions (pH 9.0) with a half-life τ1/2 ∼ 10 ms. The stability of the complexes under photocatalytic turnover conditions is probably controlled by the rate at which ligand L+ is oxidized by Co 4POM in its highest oxidation state.

AB - Hydrogen sulfate salts of [Ru(1)2]2+ where 1 = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine and four N-alkylated derivatives [Ru(L)2]4+ were used as photosensitizers (λmax ∼510 nm) for water oxidation in light driven reactions with peroxydisulfate as a sacrificial electron acceptor and Na10[Co4(H2O)2(α-PW 9O34)2] (Co4POM) as the catalyst in sodium borate buffers at pH 8.0 and 9.0. The N-substituents investigated were benzyl (L+ = 2+), ethyl (L+ = 3+), allyl (L+ = 4+) and 4-cyanobenzyl (L+ = 5 +). The O2 yield in the presence of [Ru(L) 2]4+ (L+ = 2+-4+) was comparable to that obtained in the presence [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) using light sources with λmax ≈ 490 nm. The ruthenium(iii) complexes [Ru(1)2]3+ and [Ru(L)2]5+ (L+ = 2+-5+) are rather unstable in acidic conditions and could not be isolated. The most efficient photosensitizers [Ru(L)2]5+ (L+ = 2+ and 4+) were the least stable under weakly basic conditions (pH 9.0) with a half-life τ1/2 ∼ 10 ms. The stability of the complexes under photocatalytic turnover conditions is probably controlled by the rate at which ligand L+ is oxidized by Co 4POM in its highest oxidation state.

UR - http://www.scopus.com/inward/record.url?scp=84886870970&partnerID=8YFLogxK

U2 - 10.1039/c3ra44192j

DO - 10.1039/c3ra44192j

M3 - Article

AN - SCOPUS:84886870970

SN - 2046-2069

VL - 3

SP - 20647

EP - 20654

JO - RSC Advances

JF - RSC Advances

IS - 43

ER -

Bis(4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine) ruthenium(ii) complexes and their N-alkylated derivatives in catalytic light-driven water oxidation

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