Synthesis, mixed valence aspects and non-linear optical properties of the triruthenium complexes [{(bpy)2RuII}3(L)] 3+ and [{(phen)2RuII}3(L)] 3+ (bpy = 2,2′-bipyridine, phen = 1, 10-phenanthroIine and L3- = 1,3,5-triazine-2,4,6-trithiol)

Sanjib Kar, Thomas A. Miller, Soma Chakraborty, Biprajit Sarkar, Biswajit Pradhan, Rajeev K. Sinha, Tapanendu Kundu, Michael D. Ward, Goutam Kumar Lahiri

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Abstract

The triruthenium complexes [{(bpy)2RuII}L] 3+ [1]3+ and [{(phen)2RuII} 3L]3+ [2]3+ have been synthesized via the reactions of [RuII(bpy)2(EtOH)2]2+ and [RuII(phen)2EtOH)2]2+ with the trisodium salt of 1,3,5-triazine-2,4,6 trithiol (Na3L) respectively. In CH3CN, the complexes [1]3+ and [2]3+exhibit three reversible one-electron redox processes corresponding to successive Ru(II)/Ru(III) couples. The 190-250 mV separation in potential between the successive Ru(II)/Ru(III) couples is indicative of moderate intermetallic electronic coupling in the mixed valence states. The bipyridine and phenanthroline based reductions are observed at -1.58, -1.86 V and -1.77, -2.01, -2.43 V versus SCE respectively. The spectroelectrochemical study on the bipyridine derivative [1]n+ (n = 3-6) in acetonitrile medium at 243 K shows a broad and relatively weak intervalence charge-transfer transition (IVCT) near 1900 nm for both the mixed valence states RuIIRu IIRuIII [1]4+ and RuIIRu IIIRuIII [1]5+, characteristic of class II behaviour. The calculated coupling constant (Vab), 560 cm -1 is also supportive of class II mixed-valence states. The electrochemically generated one-electron oxidised species [1]4+ or [2]4+ exhibits an EPR spectrum characteristic of low-spin Ru III ion in a distorted octahedral environment (g1 = 2.246, g2 = 1.993 for [1]4+ and g1 = 2.469, g 2 = 2.191 for [2]4+). The complexes are moderately strongly luminescent at 77 K. Both the complexes have also shown third order non-linear optical properties with γ = -4.5 × 10-29 esu for [1]3+ and -5.09 × 10-29 esu for [2] 3+.

Original languageEnglish
Pages (from-to)2591-2596
Number of pages6
JournalDalton Transactions
Issue number12
DOIs
Publication statusPublished - 21-06-2003

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Triazines
Optical properties
Phenanthrolines
Electrons
Intermetallics
Paramagnetic resonance
Charge transfer
Salts
Ions
Derivatives
Oxidation-Reduction
acetonitrile

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Kar, Sanjib ; Miller, Thomas A. ; Chakraborty, Soma ; Sarkar, Biprajit ; Pradhan, Biswajit ; Sinha, Rajeev K. ; Kundu, Tapanendu ; Ward, Michael D. ; Lahiri, Goutam Kumar. / Synthesis, mixed valence aspects and non-linear optical properties of the triruthenium complexes [{(bpy)2RuII}3(L)] 3+ and [{(phen)2RuII}3(L)] 3+ (bpy = 2,2′-bipyridine, phen = 1, 10-phenanthroIine and L3- = 1,3,5-triazine-2,4,6-trithiol). In: Dalton Transactions. 2003 ; No. 12. pp. 2591-2596.
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abstract = "The triruthenium complexes [{(bpy)2RuII}L] 3+ [1]3+ and [{(phen)2RuII} 3L]3+ [2]3+ have been synthesized via the reactions of [RuII(bpy)2(EtOH)2]2+ and [RuII(phen)2EtOH)2]2+ with the trisodium salt of 1,3,5-triazine-2,4,6 trithiol (Na3L) respectively. In CH3CN, the complexes [1]3+ and [2]3+exhibit three reversible one-electron redox processes corresponding to successive Ru(II)/Ru(III) couples. The 190-250 mV separation in potential between the successive Ru(II)/Ru(III) couples is indicative of moderate intermetallic electronic coupling in the mixed valence states. The bipyridine and phenanthroline based reductions are observed at -1.58, -1.86 V and -1.77, -2.01, -2.43 V versus SCE respectively. The spectroelectrochemical study on the bipyridine derivative [1]n+ (n = 3-6) in acetonitrile medium at 243 K shows a broad and relatively weak intervalence charge-transfer transition (IVCT) near 1900 nm for both the mixed valence states RuIIRu IIRuIII [1]4+ and RuIIRu IIIRuIII [1]5+, characteristic of class II behaviour. The calculated coupling constant (Vab), 560 cm -1 is also supportive of class II mixed-valence states. The electrochemically generated one-electron oxidised species [1]4+ or [2]4+ exhibits an EPR spectrum characteristic of low-spin Ru III ion in a distorted octahedral environment (g1 = 2.246, g2 = 1.993 for [1]4+ and g1 = 2.469, g 2 = 2.191 for [2]4+). The complexes are moderately strongly luminescent at 77 K. Both the complexes have also shown third order non-linear optical properties with γ = -4.5 × 10-29 esu for [1]3+ and -5.09 × 10-29 esu for [2] 3+.",
author = "Sanjib Kar and Miller, {Thomas A.} and Soma Chakraborty and Biprajit Sarkar and Biswajit Pradhan and Sinha, {Rajeev K.} and Tapanendu Kundu and Ward, {Michael D.} and Lahiri, {Goutam Kumar}",
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Synthesis, mixed valence aspects and non-linear optical properties of the triruthenium complexes [{(bpy)2RuII}3(L)] 3+ and [{(phen)2RuII}3(L)] 3+ (bpy = 2,2′-bipyridine, phen = 1, 10-phenanthroIine and L3- = 1,3,5-triazine-2,4,6-trithiol). / Kar, Sanjib; Miller, Thomas A.; Chakraborty, Soma; Sarkar, Biprajit; Pradhan, Biswajit; Sinha, Rajeev K.; Kundu, Tapanendu; Ward, Michael D.; Lahiri, Goutam Kumar.

In: Dalton Transactions, No. 12, 21.06.2003, p. 2591-2596.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis, mixed valence aspects and non-linear optical properties of the triruthenium complexes [{(bpy)2RuII}3(L)] 3+ and [{(phen)2RuII}3(L)] 3+ (bpy = 2,2′-bipyridine, phen = 1, 10-phenanthroIine and L3- = 1,3,5-triazine-2,4,6-trithiol)

AU - Kar, Sanjib

AU - Miller, Thomas A.

AU - Chakraborty, Soma

AU - Sarkar, Biprajit

AU - Pradhan, Biswajit

AU - Sinha, Rajeev K.

AU - Kundu, Tapanendu

AU - Ward, Michael D.

AU - Lahiri, Goutam Kumar

PY - 2003/6/21

Y1 - 2003/6/21

N2 - The triruthenium complexes [{(bpy)2RuII}L] 3+ [1]3+ and [{(phen)2RuII} 3L]3+ [2]3+ have been synthesized via the reactions of [RuII(bpy)2(EtOH)2]2+ and [RuII(phen)2EtOH)2]2+ with the trisodium salt of 1,3,5-triazine-2,4,6 trithiol (Na3L) respectively. In CH3CN, the complexes [1]3+ and [2]3+exhibit three reversible one-electron redox processes corresponding to successive Ru(II)/Ru(III) couples. The 190-250 mV separation in potential between the successive Ru(II)/Ru(III) couples is indicative of moderate intermetallic electronic coupling in the mixed valence states. The bipyridine and phenanthroline based reductions are observed at -1.58, -1.86 V and -1.77, -2.01, -2.43 V versus SCE respectively. The spectroelectrochemical study on the bipyridine derivative [1]n+ (n = 3-6) in acetonitrile medium at 243 K shows a broad and relatively weak intervalence charge-transfer transition (IVCT) near 1900 nm for both the mixed valence states RuIIRu IIRuIII [1]4+ and RuIIRu IIIRuIII [1]5+, characteristic of class II behaviour. The calculated coupling constant (Vab), 560 cm -1 is also supportive of class II mixed-valence states. The electrochemically generated one-electron oxidised species [1]4+ or [2]4+ exhibits an EPR spectrum characteristic of low-spin Ru III ion in a distorted octahedral environment (g1 = 2.246, g2 = 1.993 for [1]4+ and g1 = 2.469, g 2 = 2.191 for [2]4+). The complexes are moderately strongly luminescent at 77 K. Both the complexes have also shown third order non-linear optical properties with γ = -4.5 × 10-29 esu for [1]3+ and -5.09 × 10-29 esu for [2] 3+.

AB - The triruthenium complexes [{(bpy)2RuII}L] 3+ [1]3+ and [{(phen)2RuII} 3L]3+ [2]3+ have been synthesized via the reactions of [RuII(bpy)2(EtOH)2]2+ and [RuII(phen)2EtOH)2]2+ with the trisodium salt of 1,3,5-triazine-2,4,6 trithiol (Na3L) respectively. In CH3CN, the complexes [1]3+ and [2]3+exhibit three reversible one-electron redox processes corresponding to successive Ru(II)/Ru(III) couples. The 190-250 mV separation in potential between the successive Ru(II)/Ru(III) couples is indicative of moderate intermetallic electronic coupling in the mixed valence states. The bipyridine and phenanthroline based reductions are observed at -1.58, -1.86 V and -1.77, -2.01, -2.43 V versus SCE respectively. The spectroelectrochemical study on the bipyridine derivative [1]n+ (n = 3-6) in acetonitrile medium at 243 K shows a broad and relatively weak intervalence charge-transfer transition (IVCT) near 1900 nm for both the mixed valence states RuIIRu IIRuIII [1]4+ and RuIIRu IIIRuIII [1]5+, characteristic of class II behaviour. The calculated coupling constant (Vab), 560 cm -1 is also supportive of class II mixed-valence states. The electrochemically generated one-electron oxidised species [1]4+ or [2]4+ exhibits an EPR spectrum characteristic of low-spin Ru III ion in a distorted octahedral environment (g1 = 2.246, g2 = 1.993 for [1]4+ and g1 = 2.469, g 2 = 2.191 for [2]4+). The complexes are moderately strongly luminescent at 77 K. Both the complexes have also shown third order non-linear optical properties with γ = -4.5 × 10-29 esu for [1]3+ and -5.09 × 10-29 esu for [2] 3+.

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