Synthesis, characterization and photophysical properties of gold(I)-copper(I) alkynyl clusters with 1,4-bis(diphenylphosphino)butane, effect of the diphosphine ligand on luminescence characteristics

Ilya S. Krytchankou; Dmitry V. Krupenya; Vladislav V. Gurzhiy; Andrey A. Belyaev; Antti J. Karttunen; Igor O. Koshevoy; Alexei S. Melnikov; Sergey P. Tunik

doi:10.1016/j.jorganchem.2012.09.003

Synthesis, characterization and photophysical properties of gold(I)-copper(I) alkynyl clusters with 1,4-bis(diphenylphosphino)butane, effect of the diphosphine ligand on luminescence characteristics

Ilya S. Krytchankou
, Dmitry V. Krupenya
, Vladislav V. Gurzhiy
, Andrey A. Belyaev
, Antti J. Karttunen
, Igor O. Koshevoy
, Alexei S. Melnikov
, Sergey P. Tunik^*

^*Tämän työn vastaava kirjoittaja

Ei julkaistu Aalto-yliopiston affiliaatiolla

St. Petersburg State University
University of Eastern Finland

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

14 Viittaukset (Web of Science)

Abstrakti

Reactions of the {AuC2R}(n) polymer (R = -C6H4NO2, -C6H5, -C6H4Ph, -C6H4OMe, -C6H4NMe2, -C(OH) Me-2, -C6H10(OH)) with stoichiometric amount of 1,4-bis(diphenylphosphino) butane and Cu(I) ions afford the dicationic complexes of general formula [Au6Cu2(C-2-R)(6)(PPh2(CH2)(4)PPh2)(3)](PF6)(2). The compounds obtained (1-7) display common "rods-in-belt" structural motif with the "Cu-2{Au(C2R)(2)}(3)" central cluster core wrapped about by the {Au-3(Ph2P(CH2)(4)PPh2)(3)} belt. This structural pattern was revealed in solid state by X-ray crystallography and confirmed in solution using the NMR spectroscopy. The complexes 6 and 7 containing hydroxyl substituents in the alkynyl ligands demonstrate structural distortions due to hydrogen bonding inside the cluster core. All complexes studied exhibit intense phosphorescence in dichloromethane solution, the characteristics of which depend on donor ability of the alkynyl ligand substituents. Comparison of the emission wavelengths in 1-7 with those observed in the congeners based on the aromatic diphosphine (PPh2C6H4PPh2) showed considerable blue shift of the emission band maxima in the complexes under study. The theoretical DFT calculations indicated that the triplet emission in 1-7 is mainly determined by electron transitions inside the cluster core with some admixture of MLCT character, the contribution of which plays more important role compared to the analogs with aromatic diphosphine and causes the observed hypsochromic shift of emission. (C) 2012 Elsevier B. V. All rights reserved.

Alkuperäiskieli	Englanti
Sivut	65-71
Sivumäärä	7
Julkaisu	Journal of Organometallic Chemistry
Vuosikerta	723
DOI - pysyväislinkit	https://doi.org/10.1016/j.jorganchem.2012.09.003
Tila	Julkaistu - 1 tammik. 2013
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

Financial support from Saint-Petersburg State University research grant 12.37.132.2011, the Academy of Finland (grant 138560/2010, A.J.K.), University of Eastern Finland (Russian-Finnish collaborative project), and Russian Foundation for Basic Research (grant 11-03-00974-a) is gratefully acknowledged. The work was performed using scientific equipment of the Center of Shared Usage "The analytical center of nano- and biotechnologies of SPbSPU" with financial support of the Ministry of Education and Science of the Russian Federation. XRD study is carried out in the X-ray Diffraction Centre of St. Petersburg State University.

Pääsy asiakirjaan

10.1016/j.jorganchem.2012.09.003

Sormenjälki

Sukella tutkimusaiheisiin 'Synthesis, characterization and photophysical properties of gold(I)-copper(I) alkynyl clusters with 1,4-bis(diphenylphosphino)butane, effect of the diphosphine ligand on luminescence characteristics'. Ne muodostavat yhdessä ainutlaatuisen sormenjäljen.

Siteeraa tätä

Krytchankou, I. S., Krupenya, D. V., Gurzhiy, V. V., Belyaev, A. A., Karttunen, A. J., Koshevoy, I. O., Melnikov, A. S., & Tunik, S. P. (2013). Synthesis, characterization and photophysical properties of gold(I)-copper(I) alkynyl clusters with 1,4-bis(diphenylphosphino)butane, effect of the diphosphine ligand on luminescence characteristics. Journal of Organometallic Chemistry, 723, 65-71. https://doi.org/10.1016/j.jorganchem.2012.09.003

@article{b1503794c1e047088218ca98d1bd0358,

title = "Synthesis, characterization and photophysical properties of gold(I)-copper(I) alkynyl clusters with 1,4-bis(diphenylphosphino)butane, effect of the diphosphine ligand on luminescence characteristics",

abstract = "Reactions of the \{AuC2R\}(n) polymer (R = -C6H4NO2, -C6H5, -C6H4Ph, -C6H4OMe, -C6H4NMe2, -C(OH) Me-2, -C6H10(OH)) with stoichiometric amount of 1,4-bis(diphenylphosphino) butane and Cu(I) ions afford the dicationic complexes of general formula [Au6Cu2(C-2-R)(6)(PPh2(CH2)(4)PPh2)(3)](PF6)(2). The compounds obtained (1-7) display common {"}rods-in-belt{"} structural motif with the {"}Cu-2\{Au(C2R)(2)\}(3){"} central cluster core wrapped about by the \{Au-3(Ph2P(CH2)(4)PPh2)(3)\} belt. This structural pattern was revealed in solid state by X-ray crystallography and confirmed in solution using the NMR spectroscopy. The complexes 6 and 7 containing hydroxyl substituents in the alkynyl ligands demonstrate structural distortions due to hydrogen bonding inside the cluster core. All complexes studied exhibit intense phosphorescence in dichloromethane solution, the characteristics of which depend on donor ability of the alkynyl ligand substituents. Comparison of the emission wavelengths in 1-7 with those observed in the congeners based on the aromatic diphosphine (PPh2C6H4PPh2) showed considerable blue shift of the emission band maxima in the complexes under study. The theoretical DFT calculations indicated that the triplet emission in 1-7 is mainly determined by electron transitions inside the cluster core with some admixture of MLCT character, the contribution of which plays more important role compared to the analogs with aromatic diphosphine and causes the observed hypsochromic shift of emission. (C) 2012 Elsevier B. V. All rights reserved.",

keywords = "Gold, Copper, Alkynyl and phosphine ligands, Luminescence, Polynuclear compounds, LIGHT-EMITTING-DIODES, APPROXIMATE COULOMB POTENTIALS, DENSITY-FUNCTIONAL METHODS, AUXILIARY BASIS-SETS, CU-I COMPLEXES, OCTANUCLEAR, ELEMENTS, SYSTEMS, DESIGN, ATOMS",

author = "Krytchankou, \{Ilya S.\} and Krupenya, \{Dmitry V.\} and Gurzhiy, \{Vladislav V.\} and Belyaev, \{Andrey A.\} and Karttunen, \{Antti J.\} and Koshevoy, \{Igor O.\} and Melnikov, \{Alexei S.\} and Tunik, \{Sergey P.\}",

year = "2013",

month = jan,

day = "1",

doi = "10.1016/j.jorganchem.2012.09.003",

language = "English",

volume = "723",

pages = "65--71",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

}

Krytchankou, IS, Krupenya, DV, Gurzhiy, VV, Belyaev, AA, Karttunen, AJ, Koshevoy, IO, Melnikov, AS & Tunik, SP 2013, 'Synthesis, characterization and photophysical properties of gold(I)-copper(I) alkynyl clusters with 1,4-bis(diphenylphosphino)butane, effect of the diphosphine ligand on luminescence characteristics', Journal of Organometallic Chemistry, Vuosikerta 723, Sivut 65-71. https://doi.org/10.1016/j.jorganchem.2012.09.003

Synthesis, characterization and photophysical properties of gold(I)-copper(I) alkynyl clusters with 1,4-bis(diphenylphosphino)butane, effect of the diphosphine ligand on luminescence characteristics. / Krytchankou, Ilya S.; Krupenya, Dmitry V.; Gurzhiy, Vladislav V. et al.
julkaisussa: Journal of Organometallic Chemistry, Vuosikerta 723, 01.01.2013, s. 65-71.

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

TY - JOUR

T1 - Synthesis, characterization and photophysical properties of gold(I)-copper(I) alkynyl clusters with 1,4-bis(diphenylphosphino)butane, effect of the diphosphine ligand on luminescence characteristics

AU - Krytchankou, Ilya S.

AU - Krupenya, Dmitry V.

AU - Gurzhiy, Vladislav V.

AU - Belyaev, Andrey A.

AU - Karttunen, Antti J.

AU - Koshevoy, Igor O.

AU - Melnikov, Alexei S.

AU - Tunik, Sergey P.

PY - 2013/1/1

Y1 - 2013/1/1

N2 - Reactions of the {AuC2R}(n) polymer (R = -C6H4NO2, -C6H5, -C6H4Ph, -C6H4OMe, -C6H4NMe2, -C(OH) Me-2, -C6H10(OH)) with stoichiometric amount of 1,4-bis(diphenylphosphino) butane and Cu(I) ions afford the dicationic complexes of general formula [Au6Cu2(C-2-R)(6)(PPh2(CH2)(4)PPh2)(3)](PF6)(2). The compounds obtained (1-7) display common "rods-in-belt" structural motif with the "Cu-2{Au(C2R)(2)}(3)" central cluster core wrapped about by the {Au-3(Ph2P(CH2)(4)PPh2)(3)} belt. This structural pattern was revealed in solid state by X-ray crystallography and confirmed in solution using the NMR spectroscopy. The complexes 6 and 7 containing hydroxyl substituents in the alkynyl ligands demonstrate structural distortions due to hydrogen bonding inside the cluster core. All complexes studied exhibit intense phosphorescence in dichloromethane solution, the characteristics of which depend on donor ability of the alkynyl ligand substituents. Comparison of the emission wavelengths in 1-7 with those observed in the congeners based on the aromatic diphosphine (PPh2C6H4PPh2) showed considerable blue shift of the emission band maxima in the complexes under study. The theoretical DFT calculations indicated that the triplet emission in 1-7 is mainly determined by electron transitions inside the cluster core with some admixture of MLCT character, the contribution of which plays more important role compared to the analogs with aromatic diphosphine and causes the observed hypsochromic shift of emission. (C) 2012 Elsevier B. V. All rights reserved.

AB - Reactions of the {AuC2R}(n) polymer (R = -C6H4NO2, -C6H5, -C6H4Ph, -C6H4OMe, -C6H4NMe2, -C(OH) Me-2, -C6H10(OH)) with stoichiometric amount of 1,4-bis(diphenylphosphino) butane and Cu(I) ions afford the dicationic complexes of general formula [Au6Cu2(C-2-R)(6)(PPh2(CH2)(4)PPh2)(3)](PF6)(2). The compounds obtained (1-7) display common "rods-in-belt" structural motif with the "Cu-2{Au(C2R)(2)}(3)" central cluster core wrapped about by the {Au-3(Ph2P(CH2)(4)PPh2)(3)} belt. This structural pattern was revealed in solid state by X-ray crystallography and confirmed in solution using the NMR spectroscopy. The complexes 6 and 7 containing hydroxyl substituents in the alkynyl ligands demonstrate structural distortions due to hydrogen bonding inside the cluster core. All complexes studied exhibit intense phosphorescence in dichloromethane solution, the characteristics of which depend on donor ability of the alkynyl ligand substituents. Comparison of the emission wavelengths in 1-7 with those observed in the congeners based on the aromatic diphosphine (PPh2C6H4PPh2) showed considerable blue shift of the emission band maxima in the complexes under study. The theoretical DFT calculations indicated that the triplet emission in 1-7 is mainly determined by electron transitions inside the cluster core with some admixture of MLCT character, the contribution of which plays more important role compared to the analogs with aromatic diphosphine and causes the observed hypsochromic shift of emission. (C) 2012 Elsevier B. V. All rights reserved.

KW - Gold

KW - Copper

KW - Alkynyl and phosphine ligands

KW - Luminescence

KW - Polynuclear compounds

KW - LIGHT-EMITTING-DIODES

KW - APPROXIMATE COULOMB POTENTIALS

KW - DENSITY-FUNCTIONAL METHODS

KW - AUXILIARY BASIS-SETS

KW - CU-I COMPLEXES

KW - OCTANUCLEAR

KW - ELEMENTS

KW - SYSTEMS

KW - DESIGN

KW - ATOMS

U2 - 10.1016/j.jorganchem.2012.09.003

DO - 10.1016/j.jorganchem.2012.09.003

M3 - Article

SN - 0022-328X

VL - 723

SP - 65

EP - 71

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Krytchankou IS, Krupenya DV, Gurzhiy VV, Belyaev AA, Karttunen AJ, Koshevoy IO et al. Synthesis, characterization and photophysical properties of gold(I)-copper(I) alkynyl clusters with 1,4-bis(diphenylphosphino)butane, effect of the diphosphine ligand on luminescence characteristics. Journal of Organometallic Chemistry. 2013 tammik. 1;723:65-71. doi: 10.1016/j.jorganchem.2012.09.003