Supramolecular Construction of Cyanide-Bridged ReI Diimine Multichromophores

Kristina S. Kisel, Alexei S. Melnikov, Elena V. Grachova, Antti J. Karttunen, Antonio Doménech-Carbó, Kirill Yu Monakhov, Valentin G. Semenov, Sergey P. Tunik, Igor O. Koshevoy

Research output

Abstract

The reactions of labile [Re(diimine)(CO)3(H2O)]+ precursors (diimine = 2,2′-bipyridine, bpy; 1,10-phenanthroline, phen) with dicyanoargentate anion produce the dirhenium cyanide-bridged compounds [{Re(diimine)(CO)3}2CN)]+ (1 and 2). Substitution of the axial carbonyl ligands in 2 for triphenylphosphine gives the derivative [{Re(phen)(CO)2(PPh3)}2CN]+ (3), while the employment of a neutral metalloligand [Au(PPh3)(CN)] affords heterobimetallic complex [{Re(phen)(CO)3}NCAu(PPh3)]+ (4). Furthermore, the utilization of [Au(CN)2]-, [Pt(CN)4]2-, and [Fe(CN)6]4-/3- cyanometallates leads to the higher nuclearity aggregates [{Re(diimine)(CO)3NC}xM]m+ (M = Au, x = 2, 5 and 6; Pt, x = 4, 7 and 8; Fe, x = 6, 9 and 10). All novel compounds were characterized crystallographically. Assemblies 1-8 are phosphorescent both in solution and in the solid state; according to the DFT analysis, the optical properties are mainly associated with charge transfer from Re tricarbonyl motif to the diimine fragment. The energy of this process can be substantially modified by the properties of the ancillary ligands that allows to attain near-IR emission for 3 (λem = 737 nm in CH2Cl2). The Re-FeII/III complexes 9 and 10 are not luminescent but exhibit low energy absorptions, reaching 846 nm (10) due to ReI → FeIII transition.

Original languageEnglish
Pages (from-to)1988-2000
Number of pages13
JournalInorganic Chemistry
Volume58
Issue number3
DOIs
Publication statusPublished - 4 Feb 2019

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Cyanides
cyanides
Carbon Monoxide
ligands
energy absorption
assemblies
charge transfer
fragments
substitutes
anions
solid state
Bridged-Ring Compounds
optical properties
Ligands
Energy absorption
Discrete Fourier transforms
Anions
Charge transfer
Substitution reactions
Optical properties

Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Kisel, Kristina S. ; Melnikov, Alexei S. ; Grachova, Elena V. ; Karttunen, Antti J. ; Doménech-Carbó, Antonio ; Monakhov, Kirill Yu ; Semenov, Valentin G. ; Tunik, Sergey P. ; Koshevoy, Igor O. / Supramolecular Construction of Cyanide-Bridged ReI Diimine Multichromophores. In: Inorganic Chemistry. 2019 ; Vol. 58, No. 3. pp. 1988-2000.
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title = "Supramolecular Construction of Cyanide-Bridged ReI Diimine Multichromophores",
abstract = "The reactions of labile [Re(diimine)(CO)3(H2O)]+ precursors (diimine = 2,2′-bipyridine, bpy; 1,10-phenanthroline, phen) with dicyanoargentate anion produce the dirhenium cyanide-bridged compounds [{Re(diimine)(CO)3}2CN)]+ (1 and 2). Substitution of the axial carbonyl ligands in 2 for triphenylphosphine gives the derivative [{Re(phen)(CO)2(PPh3)}2CN]+ (3), while the employment of a neutral metalloligand [Au(PPh3)(CN)] affords heterobimetallic complex [{Re(phen)(CO)3}NCAu(PPh3)]+ (4). Furthermore, the utilization of [Au(CN)2]-, [Pt(CN)4]2-, and [Fe(CN)6]4-/3- cyanometallates leads to the higher nuclearity aggregates [{Re(diimine)(CO)3NC}xM]m+ (M = Au, x = 2, 5 and 6; Pt, x = 4, 7 and 8; Fe, x = 6, 9 and 10). All novel compounds were characterized crystallographically. Assemblies 1-8 are phosphorescent both in solution and in the solid state; according to the DFT analysis, the optical properties are mainly associated with charge transfer from Re tricarbonyl motif to the diimine fragment. The energy of this process can be substantially modified by the properties of the ancillary ligands that allows to attain near-IR emission for 3 (λem = 737 nm in CH2Cl2). The Re-FeII/III complexes 9 and 10 are not luminescent but exhibit low energy absorptions, reaching 846 nm (10) due to ReI → FeIII transition.",
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Supramolecular Construction of Cyanide-Bridged ReI Diimine Multichromophores. / Kisel, Kristina S.; Melnikov, Alexei S.; Grachova, Elena V.; Karttunen, Antti J.; Doménech-Carbó, Antonio; Monakhov, Kirill Yu; Semenov, Valentin G.; Tunik, Sergey P.; Koshevoy, Igor O.

In: Inorganic Chemistry, Vol. 58, No. 3, 04.02.2019, p. 1988-2000.

Research output

TY - JOUR

T1 - Supramolecular Construction of Cyanide-Bridged ReI Diimine Multichromophores

AU - Kisel, Kristina S.

AU - Melnikov, Alexei S.

AU - Grachova, Elena V.

AU - Karttunen, Antti J.

AU - Doménech-Carbó, Antonio

AU - Monakhov, Kirill Yu

AU - Semenov, Valentin G.

AU - Tunik, Sergey P.

AU - Koshevoy, Igor O.

PY - 2019/2/4

Y1 - 2019/2/4

N2 - The reactions of labile [Re(diimine)(CO)3(H2O)]+ precursors (diimine = 2,2′-bipyridine, bpy; 1,10-phenanthroline, phen) with dicyanoargentate anion produce the dirhenium cyanide-bridged compounds [{Re(diimine)(CO)3}2CN)]+ (1 and 2). Substitution of the axial carbonyl ligands in 2 for triphenylphosphine gives the derivative [{Re(phen)(CO)2(PPh3)}2CN]+ (3), while the employment of a neutral metalloligand [Au(PPh3)(CN)] affords heterobimetallic complex [{Re(phen)(CO)3}NCAu(PPh3)]+ (4). Furthermore, the utilization of [Au(CN)2]-, [Pt(CN)4]2-, and [Fe(CN)6]4-/3- cyanometallates leads to the higher nuclearity aggregates [{Re(diimine)(CO)3NC}xM]m+ (M = Au, x = 2, 5 and 6; Pt, x = 4, 7 and 8; Fe, x = 6, 9 and 10). All novel compounds were characterized crystallographically. Assemblies 1-8 are phosphorescent both in solution and in the solid state; according to the DFT analysis, the optical properties are mainly associated with charge transfer from Re tricarbonyl motif to the diimine fragment. The energy of this process can be substantially modified by the properties of the ancillary ligands that allows to attain near-IR emission for 3 (λem = 737 nm in CH2Cl2). The Re-FeII/III complexes 9 and 10 are not luminescent but exhibit low energy absorptions, reaching 846 nm (10) due to ReI → FeIII transition.

AB - The reactions of labile [Re(diimine)(CO)3(H2O)]+ precursors (diimine = 2,2′-bipyridine, bpy; 1,10-phenanthroline, phen) with dicyanoargentate anion produce the dirhenium cyanide-bridged compounds [{Re(diimine)(CO)3}2CN)]+ (1 and 2). Substitution of the axial carbonyl ligands in 2 for triphenylphosphine gives the derivative [{Re(phen)(CO)2(PPh3)}2CN]+ (3), while the employment of a neutral metalloligand [Au(PPh3)(CN)] affords heterobimetallic complex [{Re(phen)(CO)3}NCAu(PPh3)]+ (4). Furthermore, the utilization of [Au(CN)2]-, [Pt(CN)4]2-, and [Fe(CN)6]4-/3- cyanometallates leads to the higher nuclearity aggregates [{Re(diimine)(CO)3NC}xM]m+ (M = Au, x = 2, 5 and 6; Pt, x = 4, 7 and 8; Fe, x = 6, 9 and 10). All novel compounds were characterized crystallographically. Assemblies 1-8 are phosphorescent both in solution and in the solid state; according to the DFT analysis, the optical properties are mainly associated with charge transfer from Re tricarbonyl motif to the diimine fragment. The energy of this process can be substantially modified by the properties of the ancillary ligands that allows to attain near-IR emission for 3 (λem = 737 nm in CH2Cl2). The Re-FeII/III complexes 9 and 10 are not luminescent but exhibit low energy absorptions, reaching 846 nm (10) due to ReI → FeIII transition.

KW - RHENIUM(I) TRICARBONYL COMPLEXES

KW - DENSITY-FUNCTIONAL METHODS

KW - EXCITED-STATE

KW - COORDINATION POLYMERS

KW - SPECTROSCOPIC PROPERTIES

KW - PHOTOPHYSICAL PROPERTIES

KW - CARBONYL-COMPLEXES

KW - MULTIPLE EMISSIONS

KW - LUMINESCENT RE(I)

KW - CRYSTAL-STRUCTURE

UR - http://www.scopus.com/inward/record.url?scp=85061038055&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/supramolecular-construction-cyanidebridged-rei-diimine-multichromophores

U2 - 10.1021/acs.inorgchem.8b02974

DO - 10.1021/acs.inorgchem.8b02974

M3 - Article

C2 - 30633505

AN - SCOPUS:85061038055

VL - 58

SP - 1988

EP - 2000

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 3

ER -