Porphyrin sensitization of circularly polarised near-IR lanthanide luminescence: enhanced emission with nucleic acid binding

Abstract

A palladium porphyrin has been covalently linked to a chiral lanthanide complex and effectively sensitises near-IR emission from Nd and Yb; sensitisation is enhanced in the absence of oxygen and in the presence of a nucleic acid.

Lanthanide Assemblies and Polymetallic Complexes

“…The significant differences in coordination chemistry between the d-block and the lanthanides mean that the preparation of kinetically robust lanthanide complexes bearing d-block chromophores is relatively straightforward, and requires a ligand domain consistent with lanthanide binding. Early approaches to systems such as 19-21 relied upon the stability of a transition metal complex bearing additional binding sites, and were prepared by addition of the lanthanide as the final stage in the synthetic pathway [51][52][53][54]. This represents an effective approach, and it has been extended to the preparation of metallostars bearing six lanthanide ions around a ruthenium centre [55].…”

Luminescent Chemical and Physical Sensors Based on Lanthanide Complexes

“…In case of these complexes, the luminescence response is usually based on interactions of the analyte with the antenna ligand system, which bears a corresponding receptor unit. Moreover, intercalators for DNA have been designed on the basis of such mixed f-d metal complexes [11,12].…”

“…There are only very rare examples of probes containing Yb 3+ or Nd 3+ , all emitting in the near infrared [11,12]. At this point it is also helpful to emphasize the commonly acknowledged definition of a chemical sensor, the so-called Cambridge definition [13]:…”

Towards inert and preorganized d-block-containing receptors for trivalent lanthanides: The synthesis and characterization of triple-helical monometallic OsII and bimetallic OsII–LnIII complexes

“…Finally, DG solv refer to solvation energies in acetonitrile, which can be reasonably estimated with the original Born equation (8) for large molecular ions (e r = 36.1 is the relative dielectric permittivity in acetonitrile, z is the charge of the ion and q is the pseudospherical radius of the ion in the gas phase). 30 (8) As…”

“…g ) obtained by diffusion ordered NMR spectroscopy (5 × 10 −4 M) in acetonitrile and using the StokesEinstein equation (9) (R = 8.31 J mol −1 is the molar gas constant and g = 3.60 × 10 −4 N s m −2 is the viscosity of acetonitrile at 298 K; g ) (L = bipy, L1) can be used as a reasonable approximation for the pseudo-spherical ionic radii of the four incriminated complexes, from which the solvation energies tabulated in Table 5 can be calculated with eqn (8 …”