Table
2
Emission dissymmetry factors, gem
(Ln = Eu, Tb, 1 : 1 MeOH/H2O; 295 K)
,
for [Ln.L3]
(Rint = 0.0457) which were used in all calculations. The final R1-value
0.0434, wR(F2) 0.1219 (all data); C42H42N6O6P3Yb, M = 992.77,
monoclinic, a = 14.9462(4) A, b = 22.5220(6) A, c = 15.8151(4) A,
b = 111.917(10)1, U = 4938.9(2) A3, space group P21/n (no. 14), Z =
4, 97 376 reflections measured, 13 133 unique (Rint = 0.0662) which
were used in all calculations. The final R1-value 0.0322, wR(F2) 0.0954 (all
data); C42H42N6O6P3Nd, M = 963.97, monoclinic, a = 15.1667(5) A,
b = 22.6624(6) A, c = 15.9874(6) A, b = 112.584(4)1, U =
gem(Tb)
gem(Eu)
l/nm 539 543 548 620 622; 595 600 658 708 713
D
L
+0.16 ꢀ0.25+0.32+0.28 ꢀ0.32; +0.18 +0.33 ꢀ0.25+0.31 ꢀ0.37
ꢀ0.15+0.25 ꢀ0.31 ꢀ0.28+0.31; ꢀ0.18 ꢀ0.33+0.27 ꢀ0.31+0.40
5073.7(3) A3, 68 627 reflections measured, 13 469 unique (Rint
=
0.0704) which were used in all calculations. The final R1-value
0.0457, wR(F2) 0.1320 (all data); C42H42N6O6P3Eu, M = 971.69,
monoclinic, a = 15.0740(7) A, b = 22.6062(5) A, c = 15.9852(7) A,
b = 112.233(6)1, U = 5042.2(3) A3, 45 285 reflections measured,
12 135 unique (Rint = 0.0292) which were used in all calculations.
The final R1-value 0.0314, wR(F2) 0.0748 (all data).
second sphere of hydration.11 Furthermore, the emission
intensity of [Eu.L3] varied by less than 5% over 24 h in the
presence of a million fold excess of EDTA or aqueous MnCl2,
consistent with the effective steric shielding of the lanthanide
ion afforded by the ligand inhibiting ligand exchange and
energy transfer quenching respectively. The CPL spectraw of
each resolved complex exhibited mirror-image forms (Fig. 3),
with emission dissymmetry factors, gem, of up to 0.4 (Table 2).
The CPL spectra for SSS-D-[Eu.L3] exhibited a sign sequence
for transitions in the DJ = 1 and DJ = 2 manifolds, around
590 and 620 nm, similar to that observed with enantiopure
C4-symmetric D Eu tetra-amide complexes with an N4O4
donor set,12 consistent with the configuration assigned by CD.
In conclusion, these model C3-symmetric complexes exhibit
features that render them highly suitable as the basis for
devising emissive probes for use in CPL and time-resolved
spectroscopic applications. The ease of introduction of
different substituents at phosphorus1 and at the 4-position of
the pyridyl ring2 allows tuning of complex hydrophilicity
and absorption spectral properties, for example permitting
excitation in the range 337 to 365 nm.
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We thank CISbio Bioassays (JWW) and the ERC (FCC
266804) for support, and Dr Bob Peacock (Glasgow University)
for assistance with CPL measurements.
We dedicate this communication to the memory of our
colleague in Durham, Dr Andres Goeta.
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Notes and references
z Crystal Data. All complexes are iso-structural (monoclinic, space
group P21/n, Z = 4) and contain a number of severely disordered
solvent molecules. C42H42N6O6P3Ho, M = 984.66, monoclinic, a =
15.0447(3) A, b = 22.5125(5) A, c = 15.8446(3) A, b = 112.163(10)1,
U = 4969.96(18) A3, space group P21/n (no. 14), Z = 4, 75 633
reflections measured, 13 212 unique (Rint = 0.0403) which were used in
all calculations. The final R1-value 0.0286 wR(F2) 0.0709 (all data);
C42H42N6O6P3Sm, M = 970.08, monoclinic, a = 15.0707(4) A, b =
22.5655(5) A, c = 15.9329(4) A, b = 112.336(10)1, U = 5011.9(2) A3,
space group P21/n (no. 14), Z = 4, 63 529 reflections measured, 13 297
unique (Rint = 0.0687) which were used in all calculations. The final
R1-value 0.0398 wR(F2) 0.0965 (all data); C42H42N6O6P3Tm, M =
988.66, monoclinic, a = 14.9636(4) A, b = 22.5457(6) A, c =
15.8430(4) A, b = 111.991(10)1, U = 4956.0(2) A3, space group
P21/n (no. 14), Z = 4, 93 763 reflections measured, 13 155 unique
12 R. S. Dickins, J. A. K. Howard, C. L. Maupin, J. M. Moloney,
D. Parker, J. P. Riehl, G. Siligardi and J. A. G. Williams,
Chem.–Eur. J., 1999, 5, 1095; J. I. Bruce, S. Lopinski, D. Parker
and R. D. Peacock, Chirality, 2002, 14, 562.
c
This journal is The Royal Society of Chemistry 2011
Chem. Commun., 2011, 47, 12289–12291 12291