TY - JOUR

T1 - Rhenium fac-tricarbonyl bisimine complexes

T2 - luminescence modulation by hydrophobically driven intramolecular interactions

AU - Coogan, Michael

AU - Fernandez-Moreira, Vanesa

AU - Hess, Jacob B.

AU - Pope, Simon J. A.

AU - Williams, Craig

PY - 2009

Y1 - 2009

N2 - A triplet metal-to-ligand charge transfer emitting cationic ReI complex (1c) functionalised with a C12 alkyl chain possesses unique solvent-dependent photophysical properties. In acetonitrile solution the luminescence properties of 1c are typical of related fac-{Re(CO)3(diimine)L}+ species with emission at 555 nm (τ = 135 ns, Φem = 1.7%) whereas in water, emission was blue-shifted to 523 nm with an increase in luminescence lifetime (688 ns) and quantum yield (9.2%). These unusual properties are attributed to a dynamic intramolecular mechanism involving fold-back of the alkyl chain onto or around the coordinated 2,2′-bipyridine ligand, thus shielding the excited state from the surrounding water solvent. Comparison of 1c with ReI complexes either lacking a chain or incorporating varying chain lengths (C8 and C16) showed these properties to be unique to 1c. The intramolecular fold-back conformation was shown to be highly temperature dependent between 278 and 318 K, with elevated temperatures resulting in far less effective shielding. These unique photophysical properties can therefore be exploited in aqueous environments through interaction with lipophilic entities such as liposomes or biomolecules such as human serum albumin, which both result in a reverted red-shifted emission for 1c at 552–555 nm.

AB - A triplet metal-to-ligand charge transfer emitting cationic ReI complex (1c) functionalised with a C12 alkyl chain possesses unique solvent-dependent photophysical properties. In acetonitrile solution the luminescence properties of 1c are typical of related fac-{Re(CO)3(diimine)L}+ species with emission at 555 nm (τ = 135 ns, Φem = 1.7%) whereas in water, emission was blue-shifted to 523 nm with an increase in luminescence lifetime (688 ns) and quantum yield (9.2%). These unusual properties are attributed to a dynamic intramolecular mechanism involving fold-back of the alkyl chain onto or around the coordinated 2,2′-bipyridine ligand, thus shielding the excited state from the surrounding water solvent. Comparison of 1c with ReI complexes either lacking a chain or incorporating varying chain lengths (C8 and C16) showed these properties to be unique to 1c. The intramolecular fold-back conformation was shown to be highly temperature dependent between 278 and 318 K, with elevated temperatures resulting in far less effective shielding. These unique photophysical properties can therefore be exploited in aqueous environments through interaction with lipophilic entities such as liposomes or biomolecules such as human serum albumin, which both result in a reverted red-shifted emission for 1c at 552–555 nm.

U2 - 10.1039/B819453J

DO - 10.1039/B819453J

M3 - Journal article

VL - 33

SP - 1094

EP - 1099

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 5

ER -