TY - JOUR

T1 - A Rare Type of Rhenium(I) Diimine Complexes with Unsupported Coordinated Phosphine Oxide Ligands

T2 - Synthesis, Structural Characterization, Photophysical and Theoretical Study

AU - Nayeri, Sara

AU - Jamali, Sirous

AU - Pavlovskiy, Vladimir V.

AU - Porsev, Vitaly V.

AU - Evarestov, Robert A.

AU - Kisel, Kristina S.

AU - Koshevoy, Igor O.

AU - Shakirova, Julia R.

AU - Tunik, Sergey P.

PY - 2019/10/31

Y1 - 2019/10/31

N2 - This paper presents synthesis and photophysical investigation of a very rare type of the ReI diimine complexes, [Re(diimine)(CO)3(OPR3)]+, R = Ph, Cy; diimine – phenanthroline and neocuproine, containing monodentate (unsupported) phosphine oxide ligands. The obtained compounds have been structurally characterized in solid phase by using XRD crystallography, which revealed unusual distortions in the pseudo octahedral rhenium environment, which may be ascribed to intramolecular interligand (phosphine oxide – diimine) interaction rather than to crystal packing effect. Optimization of the ground state structure of these molecules with the DFT method also confirmed intramolecular origin of the observed structural peculiarities. The complexes display phosphorescence in solution and in solid state with the quantum yield up to 11 % and 14 %, respectively, which originates from 3MLCT excited state as demonstrated by DFT calculations. Comparative analysis of the ligand (L) effect onto emission energy in the [Re(neocuproine)(CO)3(L)] complexes (L = PPh3, NCMe, OPPh3, Cl–) showed that the position of emission wavelength in the corresponding complexes qualitatively correlates with cumulative donor ability of these ligands that is in complete agreement with the 3MLCT character of emission.

AB - This paper presents synthesis and photophysical investigation of a very rare type of the ReI diimine complexes, [Re(diimine)(CO)3(OPR3)]+, R = Ph, Cy; diimine – phenanthroline and neocuproine, containing monodentate (unsupported) phosphine oxide ligands. The obtained compounds have been structurally characterized in solid phase by using XRD crystallography, which revealed unusual distortions in the pseudo octahedral rhenium environment, which may be ascribed to intramolecular interligand (phosphine oxide – diimine) interaction rather than to crystal packing effect. Optimization of the ground state structure of these molecules with the DFT method also confirmed intramolecular origin of the observed structural peculiarities. The complexes display phosphorescence in solution and in solid state with the quantum yield up to 11 % and 14 %, respectively, which originates from 3MLCT excited state as demonstrated by DFT calculations. Comparative analysis of the ligand (L) effect onto emission energy in the [Re(neocuproine)(CO)3(L)] complexes (L = PPh3, NCMe, OPPh3, Cl–) showed that the position of emission wavelength in the corresponding complexes qualitatively correlates with cumulative donor ability of these ligands that is in complete agreement with the 3MLCT character of emission.

KW - Density functional calculations

KW - Luminescence

KW - N ligands

KW - Phosphine oxide

KW - Rhenium

KW - OXIDATION

KW - ELECTRON

KW - TRANSITION-METAL-COMPLEXES

KW - PO BOND

KW - TRICARBONYL COMPLEXES

KW - CARBONYL-COMPLEXES

KW - MANGANESE

KW - RE(I)

KW - DIPHOSPHINE

KW - CHEMISTRY

UR - http://www.scopus.com/inward/record.url?scp=85073947535&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/rare-type-rheniumi-diimine-complexes-unsupported-coordinated-phosphine-oxide-ligands-synthesis-struc

U2 - 10.1002/ejic.201900617

DO - 10.1002/ejic.201900617

M3 - Article

AN - SCOPUS:85073947535

VL - 2019

SP - 4350

EP - 4357

JO - Berichte der deutschen chemischen Gesellschaft

JF - Berichte der deutschen chemischen Gesellschaft

SN - 0365-9496

IS - 39-40

ER -