Oligophosphine-thiocyanate Copper(I) and Silver(I) Complexes and Their Borane Derivatives Showing Delayed Fluorescence

Gomathy Chakkaradhari, Toni Eskelinen, Cecilia Degbe, Andrey Belyaev, Alexey S. Melnikov, Elena V. Grachova, Sergey P. Tunik, Pipsa Hirva, Igor O. Koshevoy

Research output

4 Citations (Scopus)

Abstract

The series of chelating phosphine ligands, which contain bidentate P2 (bis[(2-diphenylphosphino)phenyl] ether, DPEphos; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, Xantphos; 1,2-bis(diphenylphosphino)benzene, dppb), tridentate P3 (bis(2-diphenylphosphinophenyl)phenylphosphine), and tetradentate P4 (tris(2-diphenylphosphino)phenylphosphine) ligands, was used for the preparation of the corresponding dinuclear [M(μ2-SCN)P2]2 (M = Cu, 1, 3, 5; M = Ag, 2, 4, 6) and mononuclear [CuNCS(P3/P4)] (7, 9) and [AgSCN(P3/P4)] (8, 10) complexes. The reactions of P4 with silver salts in a 1:2 molar ratio produce tetranuclear clusters [Ag2(μ3-SCN)(t-SCN)(P4)]2 (11) and [Ag2(μ3-SCN)(P4)]22+ (12). Complexes 7-11 bearing terminally coordinated SCN ligands were efficiently converted into derivatives 13-17 with the weakly coordinating -SCN:B(C6F5)3 isothiocyanatoborate ligand. Compounds 1 and 5-17 exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. The excited states of thiocyanate species are dominated by the ligand to ligand SCN → π(phosphine) charge transfer transitions mixed with a variable contribution of MLCT. The boronation of SCN groups changes the nature of both the S1 and T1 states to (L + M)LCT d,p(M, P) → π(phosphine). The localization of the excited states on the aromatic systems of the phosphine ligands determines a wide range of luminescence energies achieved for the title complexes (λem varies from 448 nm for 1 to 630 nm for 10c). The emission of compounds 10 and 15, based on the P4 ligand, strongly depends on the solid-state packing (λem = 505 and 625 nm for two crystalline forms of 15), which affects structural reorganizations accompanying the formation of electronically excited states.

Original languageEnglish
Pages (from-to)3646-3660
Number of pages15
JournalInorganic Chemistry
Volume58
Issue number6
DOIs
Publication statusPublished - 18 Mar 2019

Fingerprint

Boranes
phosphine
boranes
Silver
Fluorescence
silver
Ligands
Derivatives
copper
fluorescence
ligands
phosphines
Excited states
Bearings (structural)
excitation
solid state
cuprous thiocyanate
Chelation
Charge transfer
Luminescence

Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Chakkaradhari, Gomathy ; Eskelinen, Toni ; Degbe, Cecilia ; Belyaev, Andrey ; Melnikov, Alexey S. ; Grachova, Elena V. ; Tunik, Sergey P. ; Hirva, Pipsa ; Koshevoy, Igor O. / Oligophosphine-thiocyanate Copper(I) and Silver(I) Complexes and Their Borane Derivatives Showing Delayed Fluorescence. In: Inorganic Chemistry. 2019 ; Vol. 58, No. 6. pp. 3646-3660.
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title = "Oligophosphine-thiocyanate Copper(I) and Silver(I) Complexes and Their Borane Derivatives Showing Delayed Fluorescence",
abstract = "The series of chelating phosphine ligands, which contain bidentate P2 (bis[(2-diphenylphosphino)phenyl] ether, DPEphos; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, Xantphos; 1,2-bis(diphenylphosphino)benzene, dppb), tridentate P3 (bis(2-diphenylphosphinophenyl)phenylphosphine), and tetradentate P4 (tris(2-diphenylphosphino)phenylphosphine) ligands, was used for the preparation of the corresponding dinuclear [M(μ2-SCN)P2]2 (M = Cu, 1, 3, 5; M = Ag, 2, 4, 6) and mononuclear [CuNCS(P3/P4)] (7, 9) and [AgSCN(P3/P4)] (8, 10) complexes. The reactions of P4 with silver salts in a 1:2 molar ratio produce tetranuclear clusters [Ag2(μ3-SCN)(t-SCN)(P4)]2 (11) and [Ag2(μ3-SCN)(P4)]22+ (12). Complexes 7-11 bearing terminally coordinated SCN ligands were efficiently converted into derivatives 13-17 with the weakly coordinating -SCN:B(C6F5)3 isothiocyanatoborate ligand. Compounds 1 and 5-17 exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. The excited states of thiocyanate species are dominated by the ligand to ligand SCN → π(phosphine) charge transfer transitions mixed with a variable contribution of MLCT. The boronation of SCN groups changes the nature of both the S1 and T1 states to (L + M)LCT d,p(M, P) → π(phosphine). The localization of the excited states on the aromatic systems of the phosphine ligands determines a wide range of luminescence energies achieved for the title complexes (λem varies from 448 nm for 1 to 630 nm for 10c). The emission of compounds 10 and 15, based on the P4 ligand, strongly depends on the solid-state packing (λem = 505 and 625 nm for two crystalline forms of 15), which affects structural reorganizations accompanying the formation of electronically excited states.",
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author = "Gomathy Chakkaradhari and Toni Eskelinen and Cecilia Degbe and Andrey Belyaev and Melnikov, {Alexey S.} and Grachova, {Elena V.} and Tunik, {Sergey P.} and Pipsa Hirva and Koshevoy, {Igor O.}",
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Oligophosphine-thiocyanate Copper(I) and Silver(I) Complexes and Their Borane Derivatives Showing Delayed Fluorescence. / Chakkaradhari, Gomathy; Eskelinen, Toni; Degbe, Cecilia; Belyaev, Andrey; Melnikov, Alexey S.; Grachova, Elena V.; Tunik, Sergey P.; Hirva, Pipsa; Koshevoy, Igor O.

In: Inorganic Chemistry, Vol. 58, No. 6, 18.03.2019, p. 3646-3660.

Research output

TY - JOUR

T1 - Oligophosphine-thiocyanate Copper(I) and Silver(I) Complexes and Their Borane Derivatives Showing Delayed Fluorescence

AU - Chakkaradhari, Gomathy

AU - Eskelinen, Toni

AU - Degbe, Cecilia

AU - Belyaev, Andrey

AU - Melnikov, Alexey S.

AU - Grachova, Elena V.

AU - Tunik, Sergey P.

AU - Hirva, Pipsa

AU - Koshevoy, Igor O.

PY - 2019/3/18

Y1 - 2019/3/18

N2 - The series of chelating phosphine ligands, which contain bidentate P2 (bis[(2-diphenylphosphino)phenyl] ether, DPEphos; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, Xantphos; 1,2-bis(diphenylphosphino)benzene, dppb), tridentate P3 (bis(2-diphenylphosphinophenyl)phenylphosphine), and tetradentate P4 (tris(2-diphenylphosphino)phenylphosphine) ligands, was used for the preparation of the corresponding dinuclear [M(μ2-SCN)P2]2 (M = Cu, 1, 3, 5; M = Ag, 2, 4, 6) and mononuclear [CuNCS(P3/P4)] (7, 9) and [AgSCN(P3/P4)] (8, 10) complexes. The reactions of P4 with silver salts in a 1:2 molar ratio produce tetranuclear clusters [Ag2(μ3-SCN)(t-SCN)(P4)]2 (11) and [Ag2(μ3-SCN)(P4)]22+ (12). Complexes 7-11 bearing terminally coordinated SCN ligands were efficiently converted into derivatives 13-17 with the weakly coordinating -SCN:B(C6F5)3 isothiocyanatoborate ligand. Compounds 1 and 5-17 exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. The excited states of thiocyanate species are dominated by the ligand to ligand SCN → π(phosphine) charge transfer transitions mixed with a variable contribution of MLCT. The boronation of SCN groups changes the nature of both the S1 and T1 states to (L + M)LCT d,p(M, P) → π(phosphine). The localization of the excited states on the aromatic systems of the phosphine ligands determines a wide range of luminescence energies achieved for the title complexes (λem varies from 448 nm for 1 to 630 nm for 10c). The emission of compounds 10 and 15, based on the P4 ligand, strongly depends on the solid-state packing (λem = 505 and 625 nm for two crystalline forms of 15), which affects structural reorganizations accompanying the formation of electronically excited states.

AB - The series of chelating phosphine ligands, which contain bidentate P2 (bis[(2-diphenylphosphino)phenyl] ether, DPEphos; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, Xantphos; 1,2-bis(diphenylphosphino)benzene, dppb), tridentate P3 (bis(2-diphenylphosphinophenyl)phenylphosphine), and tetradentate P4 (tris(2-diphenylphosphino)phenylphosphine) ligands, was used for the preparation of the corresponding dinuclear [M(μ2-SCN)P2]2 (M = Cu, 1, 3, 5; M = Ag, 2, 4, 6) and mononuclear [CuNCS(P3/P4)] (7, 9) and [AgSCN(P3/P4)] (8, 10) complexes. The reactions of P4 with silver salts in a 1:2 molar ratio produce tetranuclear clusters [Ag2(μ3-SCN)(t-SCN)(P4)]2 (11) and [Ag2(μ3-SCN)(P4)]22+ (12). Complexes 7-11 bearing terminally coordinated SCN ligands were efficiently converted into derivatives 13-17 with the weakly coordinating -SCN:B(C6F5)3 isothiocyanatoborate ligand. Compounds 1 and 5-17 exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. The excited states of thiocyanate species are dominated by the ligand to ligand SCN → π(phosphine) charge transfer transitions mixed with a variable contribution of MLCT. The boronation of SCN groups changes the nature of both the S1 and T1 states to (L + M)LCT d,p(M, P) → π(phosphine). The localization of the excited states on the aromatic systems of the phosphine ligands determines a wide range of luminescence energies achieved for the title complexes (λem varies from 448 nm for 1 to 630 nm for 10c). The emission of compounds 10 and 15, based on the P4 ligand, strongly depends on the solid-state packing (λem = 505 and 625 nm for two crystalline forms of 15), which affects structural reorganizations accompanying the formation of electronically excited states.

KW - SOLID-STATE

KW - DIPHOSPHINE LIGANDS

KW - CUPROUS COMPLEXES

KW - CU(I) COMPLEXES

KW - METAL-COMPLEXES

KW - QUANTUM YIELD

KW - CU-I

KW - PHOTOLUMINESCENCE

KW - COORDINATION

KW - FORMS

UR - http://www.scopus.com/inward/record.url?scp=85063273871&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/oligophosphinethiocyanate-copperi-silveri-complexes-borane-derivatives-showing-delayed-fluorescence

U2 - 10.1021/acs.inorgchem.8b03166

DO - 10.1021/acs.inorgchem.8b03166

M3 - Article

C2 - 30793896

AN - SCOPUS:85063273871

VL - 58

SP - 3646

EP - 3660

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 6

ER -