CHIRALITY (2014)

Review Article
Lanthanide Circularly Polarized Luminescence:
Bases and Applications
FRANCESCO ZINNA AND LORENZO DI BARI*
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Pisa, Italy

ABSTRACT Lanthanide (III) luminescence is very characteristic: it is characterized by nar-

row emission bands, large Stokes shift, and a long excited state lifetime. Moreover, chiral lantha-
nide complexes can emit strongly circularly polarized light in a way that is almost precluded to
purely organic molecules. Thanks to the sensitivity and specificity of the Ln circularly polarized
luminescence (CPL) signal, CPL-active complexes are therefore employed as bioanalytical tools
and other uses can be envisaged in many other fields. Here we present a brief overview of the
most recently developed CPL-active lanthanide complexes and a selected few examples of their
applications. We briefly discuss the main mechanisms that can rationalize the observed outstand-
ing CPL properties of these systems, and some practical suggestions on how to measure and
report data. Chirality 00:000–000, 2014. © 2014 Wiley Periodicals, Inc.

KEY WORDS: lanthanides; chiral complexes; luminescence; circularly polarized luminescence;

CPL; luminescent bioprobes; chiroptical spectroscopy; luminescence
dissymmetry factor

INTRODUCTION for biomedical imaging and sensing9 and bioanalytical applica-

Compared to d-metals, lanthanides (III) are endowed with tions13 (see below for some examples), electroluminescent de-
peculiar spectroscopic features.1–3 Their absorption and emis- vices,14–16 in photovoltaics as spectrum downshifters,17 in
sion bands are narrow and the energies of their electronic telecommunications,18 and as dyes in security inks and labels.3
transitions are largely independent of the coordination envi- In addition, when the emissive complex is chiral
ronments. They can be considered spherical emitters in solu- nonracemic, it may emit left and right circularly polarized
tion with a long excited state lifetime (up to 10 msec), so they light with different intensities. The phenomenon is called cir-
do not require taking into account emission anisotropy. cularly polarized luminescence (hereafter CPL) and it is usu-
Purely intraconfigurational f → f transitions are Laporte- ally quantified through the luminescence dissymmetry factor
forbidden and are associated with very small absorption bands glum, defined as:
(ε = 1–10 M
1 cm
1), but they can be conveniently observed in I L −I R ΔI
emission, once they reach an excited state by means of some g lum ¼ ¼ (1)
1=2ðI L þ I R Þ I
energy transfer process. Usually this is made possible through
a so-called antenna effect, which requires that the organic li- Where IL and IR are the left and right polarized emission in-
gand* absorbs high-energy radiation and passes excitation tensities, respectively. It follows immediately that glum = ±2
onto the Ln(III), most often through a Förster mechanism. means complete polarization of the emitted light while 0
Lanthanide coordination chemistry is well known,11 which corresponds to an unpolarized beam. While isolated organic
allows one to rationally design ligands containing chromo- chiral molecules or macromolecules typically display glum values
phoric groups: if the electronic levels of donor (ligand) and of 10-3–10
2, lanthanide complexes show values of 0.1–1,19
acceptor (lanthanide) match2 and if they are in close proxim- with 1.38 being the highest value ever reported so far for a
ity and with the correct lifetimes, the ligand-to-lanthanide en- lanthanide complex20 (and, to the best of our knowledge, one
ergy transfer process can be quite efficient.† of the highest values ever measured at all).
In fact, high quantum yields have been reported especially CPL allows one to:21
for Eu3+ in the visible (red) region. At the moment, one can
reasonably predict the main features of a successful complex, • extract information about the chirality of the excited
and justify a posteriori its experimental behavior. This leads state (CPL is therefore complementary to circular
to a rational ligand design, although not always the final prod- dichroism);
ucts meet expectations, because of the multiple parameters
involved in the process.
For these characteristics, luminescent Ln3+ has been
*Correspondence to: L. Di Bari, Dipartimento di Chimica e Chimica
employed for various purposes, such as:12 molecular probes Industriale, Università di Pisa, via Moruzzi 3, I-56124 Pisa, Italy. E-mail:
[email protected]
Received for publication 3 June 2014; Accepted 4 August 2014
*There are some reports of d-f dimetallic complexes where the absorbing DOI: 10.1002/chir.22382
chromophore is the d-metal.5–7 Published online in Wiley Online Library
†
This mechanism ensures large Stokes shift: 250 nm can be typical. (wileyonlinelibrary.com).
© 2014 Wiley Periodicals, Inc.
 ZINNA AND DI BARI

• observe transitions that cannot be easily observed in ab- TABLE 1. Ln3+ transitions generally observed in CPL mea-
sorption (as it is the case with f → f transitions of surements with their D class22 and their approximate
lanthanides); wavelength
• observe only selected transitions (since one may have Ion Transition Wavelength (nm) Class
many chromophores but only a few luminophores that
respond to a certain excitation wavelength). Sm3+ 4
G5/2 → 6H5/2 565 DII
4
G5/2 → 6H7/2 595 DIII
Lanthanide complexes are optimal candidates to be studied Eu3+ 5
D0 → 7 F 1 595 DI
through CPL. Tb3+ 5
D4 → 7 F 5 545 DII
Dy3+ 4
F9/2 → 6H11/2 670 DIII
In this brief review we shall discuss some recent applications
and developments of lanthanide CPL. All the following exam-
ples deal with complexes in solution: in the literature there
are only rare and relatively old examples of measurements in degenerate in a total symmetric environment: depending on
the solid state, although the current interest for applications the coordination sphere this degeneracy can be removed,26
of lanthanide luminescence in devices of various types should leading to a splitting of the emission band.
solicit more activity solid-state CPL measurements. The energy gap among these levels can be as small as 100–
130 cm
1, which translates to 5 nm or less in the yellow-
Where to Look for High glum Values orange region.
High glum values are to be sought for among electric dipole As a consequence, at room temperature this may be only
forbidden/magnetic dipole-allowed transitions. partially (if at all) resolved.
In fact, for the transition i → j the luminescence dissymme- As occurs in other spectroscopies where bands may have
try factor can be written as: different signs, and very notably in electronic and vibrational




circular dichroism (CD), in CPL there may be an apparent

μ

mji
cosθμ;m
ij
g lum ¼ 4

2

2 (2) resolution enhancement when nearby transitions have oppo-

μ
þ
mji
site rotational strengths.
ij
This is notably the case of the CPL spectrum shown in Fig. 1,
where μij and mji are the electric and magnetic transition di- concerning the 5D4 → 7 F5 transition of a Tb3+ chiral complex.27
pole vectors and θμ,m is the angle between them. In the case Clearly, when this happens, total emission and CPL bands
of an electric dipole-allowed transition, the |mji|2 term is neg- do not coincide in general and special care should be taken
ligible with respect to |μij|2; so Eq. (2) becomes: in evaluating the glum value.
mji Knowing the energies of the J levels provides useful infor-
g lum ¼ 4 cosθμ;m (3) mation about the crystal field environment, which in turn
μij
can be correlated with the polarizability of the donor groups.28
with the |mji| /|μij| ratio being well less than 1.
A strict Laporte selection rule cannot apply in chiral mole-
cules, because rotation-reflection (or rotoreflection) ele-
ments, like symmetry planes and inversion, are excluded by
chirality itself. Nonetheless, if the chromophore can be con-
sidered intrinsically achiral, then one can generally postulate
that for some of its electronic transitions μij is very small so
that glum may become sizeable (but in any case smaller than
2).
Richardson22 classified lanthanide transitions in three clas-
ses (DI, DII, and DIII) concerning the dissymmetry factor:
the magnitude of the observed dissymmetry factors is ex-
pected to decrease as DI > DII > DIII. Richardson himself
noted that the Eu3+ 5D0 → 7 F1 is the only lanthanide transi-
tion belonging to class DI easily accessible to CPL measure-
ment; no wonder that the highest glum values have been
measured for this transition.
Besides Eu3+, CPL spectra in the visible region are com-
monly measured for Sm3+,23,24 Tb3+,23,25 and Dy3+23 com-
plexes; in Table 1 we show the transitions generally
observed in CPL measurements and their D class.

CPL and Total Luminescence

Although the emission bands of most lanthanide com-
plexes are very narrow, especially compared to those of or-
ganic or d-metal emitters, very often they display a fine
structure, consisting of lines of one or a few nm width.
Taking as an example the 5D0 → 7FJ transitions associated
Fig. 1. CPL and total emission of a Tb3+ complex for 5D4 → 7 F5 transition.
with a Eu3+ complex, it can be noted that the initial state is Notice how the manifold is resolved in the CPL spectrum (reproduced with
singly degenerate, while the final state is (2 J + 1)–fold permission from Ref. 27).
Chirality DOI 10.1002/chir
 LANTHANIDE CIRCULARLY POLARIZED LUMINESCENCE

Often, Ln complexes in solution give rise to multiple spe-

cies of different symmetry and shape which may also be in-
volved in a network of equilibria: in any case the number of
lines of each term-to-term manifold cannot exceed the multi-
plicity of the final state.
In fact, before luminescence occurs, the system rearranges
to a single low-energy excited state sublevel. If the number of
apparent transitions in a given multiplet is larger than ex-
pected, this can be taken as a strong indication that there is
more than one emitting species.
For example, the observation of a single sharp band for
the 5D0 → 7 F0 transition around 580 nm is often used as an Scheme 2. Conjectural structure for the podate lanthanide complexes re-
argument in favor of the presence of a single emitting ported by Raymond and colleagues23 (Ln = Sm, Eu, Tb, Dy). The stereogenic
species. centers are homochiral and the complex was prepared and characterized with
both ligand enantiomers.
In fact, the 7 F0 level is nondegenerate and a true single
band is expected. However, this transition is usually quite
weak and the multiplicity can remain hidden within the band- with a 1-phenylethylamine substituent each, encoding the
width; moreover, owing to the small extent of spin-orbit cou- chiral information (Scheme 2).
plings and the crystal field effects which modulate the exact This ligand has proven to be particularly efficient in sensi-
wavelength of lanthanide f → f transitions, accidental degener- tizing four different Ln3+ ions,‡ namely: Sm3+, Eu3+, Tb3+,
acy of the 5D0 → 7 F0 within several (exchanging) species is and Dy3+. All these complexes display good emission and
possible, which would lead to a true single band in that region. CPL activity. Unfortunately, the geometry and the coordina-
When dealing with such a situation, it can be convenient to tion mode of these complexes remain undetermined.
excite the complex with left, right, and linearly polarized light; The same structural motif was employed to develop similar
if there is a single emitting species, no significant change of ligands, designed to provide a bigger steric hindrance and
the CPL spectrum will be visible.29 shield the Ln3+ ion from water coordination in a more effec-
tive way.37

DEVELOPMENT OF COMPLEX WITH HIGH glum β-Diketonates

VALUES Due to the oxophilicity of Ln3+ ions, β-diketonates are effec-
Macrocycles and Podates tive coordinating molecules for lanthanide ions. Through
Cyclen (L1) and its smaller relative triazacyclononane (L2, their use it is possible to prepare tetrakis complexes, which
Scheme 1) are versatile scaffolds to be functionalized at the are often moisture inert, thanks to the bidentate nature of
N-atoms with arms bearing coordinating groups such as car- the ligand: indeed, this leads to an 8-coordination number,
boxylates, amides, phosphinates, and N-donors; central chi- and to the fact that the resulting complex is anionic.§
rality elements can be introduced in the ring or, more Neutral tris species can also be prepared but their coordina-
frequently, on the side-arms at a carbon center.30–33 tion sphere must be completed by at least a molecule of water
The arms can also carry a chromophore (e.g., aryl, or other Lewis bases such as bipyridines or phenanthrolines.
heteroaryl, azaxanthones) able to sensitize the lanthanide β-diketonates are often good sensitizers for Eu3+. In
ion. These complexes have been extensively exploited as particular:
CPL probes by Parker’s group (see section below).
Podate complexes were shown to strongly bind Ln3+ ions, • the diketonate-centered π → π* transition is strong and
saturating their coordination sphere and shielding them from falls in the near-UV region; moreover, its electric dipole
other coordinating molecules, such as H2O. This makes them moment is centered in the middle of the diketonate
suitable for application in aqueous solutions; water in the first moiety;
coordination sphere can be a major issue in Ln emission, • Eu3+ ion is only 2.3–2.4 Å distant from the donor oxygen
since O-H is a high-energy oscillator and can lead to a atoms¶;11
nonradiative deactivation of the luminescence.34,35 • substituents at 1 or 3 positions can modify the absorp-
Raymond and colleagues23,25 reported the ligand L3, in tion wavelength of the diketonate and modulate the en-
which four 2-hydroxyisophthalamide pendant arms are ergy of the triplet state, in order to optimize the energy
bound to ethylendiamine; the arms are further functionalized levels involved in the ligand-to-metal energy transfer;

‡
It may be interesting to notice that the same ligand was also employed to
sensitize curium(III).36
§
It should be recalled that LnDOTA complexes are partially hydrated, de-
spite the fact that the ligand is 8-dentate and the resulting complexes an-
ionic. However, this is a function of the ionic radius of a given
lanthanide.38
¶
Two main mechanisms describe the energy transfer: Dexter and Förster
resonant energy transfer (FRET).2 Both depend strongly on the donor-
acceptor distance R: Dexter mechanism depends on e-αR, while FRET de-
Scheme 1. Cyclen (L1) and triazacyclononane (L2). pends on R
6.
Chirality DOI 10.1002/chir
 ZINNA AND DI BARI

• chiral diketones can be easily synthesized through a that in these cases the CPL activity is mainly controlled by
Claisen type reaction from cheap natural enantiopure the chirality of D-facam ligands.
ketones.
Other Diketonate-Based Chiral Complexes
Therefore, it is not surprising that many complexes with out- 1,1,1,5,5,5-Hexafluoropentane-2,4-dione (HFA, L8,
3+
standing optical and chiroptical properties belong to this class: Scheme 4) is known to be a good sensitizer for Eu . HFA
to the best of our knowledge, Eu(TTA)32 L6 (TTA = 2- has been used by Yuasa et al.46 to synthesize a series of com-
thenoyltrifluoroacetonate, L4; L5 = dibenzylsulfoxide; Scheme 3) plexes Ln(HFA)3 L* (L* = L15, L11, L12, Scheme 4) in which
displays the highest quantum yield reported for a Eu3+ complex the chiral ligand L* induces an asymmetric arrangement of
(85%) at solid state,39,40 while the heterobimetallic complex the three HFA ligands around the lanthanide.
CsEu(hfbc)4 (hfbc =heptafluorobutyrylcamphorate, L6; Scheme 3) With the reported series of Pybox ligands as L*, they ob-
showed a glum value of 1.38, the highest ever measured for an tained high luminescence quantum yields (34–41%) and glum
Ln3+ system.20,24 It should also be noted that the same ligand values (|0.15|–|0.46|) in CD3CN solution for Eu3+ complexes.
L6 was able to sensitize Sm3+, providing another complex with Interestingly enough, the signs of the 5D0 → 7 F1 and
5
excellent polarization characteristics. For the manifold associ- D0 → 7 F2 transitions were the same for L* = (R)-iPr-Pybox
ated with the Sm3+ 4G5/2 → 6H5/2 transition, Kaizaki and ((R)-L11) and (R,R)-Me-Ph-Pybox ((R,R)-L12), but they were
colleagues24 reported glum values of
1.15 (at 553 nm),
0.35 inverted for bis-4R-(4-phenyl-oxazolinyl)pyridine ((R)-Ph-
(561 nm), +0.96 (575 nm), and
0.45 (588 nm). Pybox, (R)-L15) (see Table 3 and Scheme 4).
In order to correlate the CPL spectrum signature with the
complex structure, single-crystal X-ray structural analyses
Camphor-Based Systems were performed. It was found that the ligand–ligand intramo-
Camphor provides a rigid chiral backbone employable in lecular interactions account for the asymmetric arrangement
the synthesis of β-diketones; aside from the exceptional per- around the lanthanide ion, justifying the observed CPL spec-
formances mentioned for CsEu(hfbc)4, several other trum signature. Anyway, no analysis to assess the actual
camphorate-based complexes have been investigated by structure in solution nor the possible stereoisomer equilibria
CPL spectroscopists with interesting results. was carried out. However, the CD spectra measured in solu-
Tris europium trifluoromethylcamphorate (Eu(facam)3, tion for EuL83L11 and EuL83L12 display bands with the same
facam = L7; Scheme 4) in dimethylsulphoxide displays a glum sign, while the sign is inverted for EuL83L15, consistent with
of |0.78|41 and it is used as a standard for CPL instruments cal- the solid-state data.
ibration,42 even though this practice has been recently criti- It is worth noting that the CPL of Eu(facam)3 L14 and Eu
cized and other systems have been proposed.43 (HFA)3 L15 has been investigated even at solid state. taking
Recently, Eu(facam)3 complexes with several ancillary li- the measurements on single crystals.47
gands have been synthesized and their CPL measured in
solution. Polynuclear Systems
Harada et al.44,45 employed ligands with atropos or tropos Recently, chiral polylanthanidic systems with large glum
axial chirality such as (R/S)-2,2’-bis(diphenylphosphoryl)- values have begun being synthesized.
1,10-binaphthyl ((R/S)-BINAPO, (R/S)-L9),-2,2’-bis(diphenyl- Mamula et al.48 reported a C3 trinuclear complex with a chi-
phosphoryl)-1,10-biphenyl (BIPHEBO, L10), with central ral bipyridine–carboxylate ligand (L16, Fig. 2), formed
chirality as bis-(4R/4S)-(4-isopropyl-oxazolinyl)pyridine ((R/S)- through a completely diastereoselective self-assembly pro-
i
Pr-Pybox, ((R/S)-L11), and bis-(4S,5S/4R,5R)-(4-methyl-5-phe- cess which shows also a complete chiral self-recognition in
nyl-oxazolinyl)pyridine ((S,S/R,R)-Me-Ph-Pybox, (S,S/R,R)-L12), the presence of enantiomer mixtures of the ligand, yielding
and achiral ligands as 1,10-phenanthroline (Phen, L13) and the system of formula Eu3L16 1
6 . In addition, H-NMR studies
triphenylphosphine oxide (TPPO, L14) (Scheme 4). The re- showed that the gross crystal structure of the system (see
ported glum values for the magnetic transitions in acetone-d6 Fig. 2) is preserved in CH2Cl2 solution.4 glum of |0.088|
range from |0.44| to |1.0| (Table 2). and |0.0806| were measured in CH2Cl2 for the 5D0 → 7 F1
Changing the absolute configuration of the ancillary li- and 5D4 → 7 F5 transitions of the Eu3+ and Tb3+ complexes,
gands in Eu((R/S)-BINAPO)(D-facam)3 and Eu((R/S)-iPr- respectively.
Pybox)(D-facam)3, the glum sign remains unchanged, indicating More recently, Mazzanti and colleagues10 synthesized an
Eu3+ complex with multilayered supramolecular architecture
using (S/R)-6’-(4-phenyloxazolin-2-yl)-2,2’-bipyridine-6-car-
boxylate as a ligand (L17, Fig. 3) and investigated its optical
properties.
Starting from a ligand of S (or R) chirality, one obtains a
mixture of diastereomeric Δ and Λ complexes of EuL17 2 stoi-
chiometry with only partial selectivity (Λ/Δ ≈ 1.8, with S li-
gand). In concentrated acetonitrile solution (6 mM),
complexes of formula Eu3L17 6 self-assemble with a defined
helicity (namely, Δ, with S ligand), this system displays 25%
quantum yield with a |0.45| glum value for the 5D0 → 7 F1
transition.
A controlled addition of Eu(OTf)3 leads to formation of a
Scheme 3. Two Eu3+ complexes displaying peculiar optical (Eu(TTA)32 L5, heptanuclear system displaying a 27% quantum yield with a
quantum yield = 85%), and chiroptical (CsEu(hfbc)4, glum = 1.38) features. |0.10| glum value. This glum is lower than that measured for
Chirality DOI 10.1002/chir
 LANTHANIDE CIRCULARLY POLARIZED LUMINESCENCE

Scheme 4. Diketonate-based Eu3+ complexes and ancillary ligands reported in Refs. 44–46.

TABLE 2. Ancillary ligands for Eu(D-facam)3 and glum values

of the resulting complexes measured in d6-acetone44,45 (see
Scheme 4)

Ancillary ligand glum (λ = 595 nm)

9
(R)-BINAPO ((R)-L ) 0.44
(S)-BINAPO ((S)-L9) 0.34
BIPHEBO (L10) 0.24
(R)-iPr-Pybox ((R)-L11)
1.0
(S)-iPr-Pybox ((S)-L11)
0.8
(S,S)-Me-Ph-Pybox (S,S)-L12)
1.0
Phen (L13)
0.46
TPPO (L14) 0.47

TABLE 3. Ancillary ligand for Eu(HFA)3 and glum values of the

resulting complexes measured in CD3CN46 (see Scheme 4) Fig. 2. (
)-5,6-Pinene-bipyridine ligand (L16) and the X-ray structure of
the EuL16
23 complex (reproduced with permission from Ref. 4).
Ancillary ligand glum
5 7 5
D0 → F1 D0 → 7 F 2
15
(R)-Ph-Pybox ((R)-L ) 0.15
0.020 chiroptical properties discussed above, lanthanide complexes
(R)-iPr-Pybox ((R)-L11)
0.46 0.034 have been employed as probes for small molecules and also
(R,R)-Me-Ph-Pybox ((R,R)-L12)
0.35 0.026 proteins.
Parker et al. reported a wealth of cyclen and
triazacyclenonane-based Eu3+ and Tb3+ complexes9,49–51
(Scheme 1).
the trinuclear complex; in fact, in the heptanuclear system a
central Eu3+ ion coordinates six EuL17 Lanthanide CPL and organic molecules
2 units; six of them
3+
display Δ chirality, while the other six display Λ chirality; Dynamically racemic complexes. Tb tris 2,6-pyridine-
moreover, these units come in an alternate fashion, so the dicarboxylate (L18) and chelidamic acid (L19) (Scheme 5) D3
intrinsic chirality of each EuL172 is almost balanced out in racemic complexes can interact with nonracemic compounds,
the complex (Fig. 3). giving rise to CPL.52,53 Recently, they have been employed by
Muller and colleagues54 as probes for amino acids. These are
in fact chiral D3 complexes, but Λ and Δ enantiomers undergo
LANTHANIDE CPL PROBES FOR MOLECULAR a rapid equilibrium in solution and cannot be resolved.
SENSING When they interact with enantiopure amino acids, thanks to
Thanks to the great sensitivity of the CPL signals to confor- their ability to form a hydrogen-bond network, one form pre-
mational and structural aspects and to the peculiar optical and vails over the other, since they are now in a diastereomeric
Chirality DOI 10.1002/chir
 ZINNA AND DI BARI

When α1-acid glycoprotein (α1-AGP) is added, EuL20 shows

optical activity and a CPL signal is switched on. The complex
is coordinatively unsaturated and a weakly coordinated axial
water molecule is needed to fill the coordination sphere.
The α1-AGP displaces the axial ligand and, at the same
time, it perturbs the racemic equilibrium towards one of the
two conformational enantiomers, as signaled by the change
of the total emission spectrum and mainly by the appearance
of a strong CPL signal (Fig. 4).
In particular, the glum factor of the 5D0 → 7 F1 transition in-
creases upon adding the protein, allowing one to estimate a
binding constant for the system formed by EuL20 and α1-AGP.
Given the selectivity of the CPL response to α1-AGP, this
and similar systems pave the way to the development of an
Fig. 3. Top: (S)-6’-(4-phenyloxazolin-2-yl)-2,2’-bipyridine-6-carboxylate analytical method to track this protein: the importance of
(L17) ligand. Bottom: the XRD structure of the heptanuclear complex, where monitoring α1-AGP levels in serum has been recently recog-
the units yellow and green represent Δ and Λ mononuclear complexes nized, because it increases as a response to an inflammatory
EuL17
2 , respectively (reproduced with permission from Ref. 10. Copyright
2012 American Chemical Society). acute state and can be used as a biomarker for breast cancer.

Enantiopure complexes. Enantiopure complexes are endowed

with intrinsic CPL, which can be modified in both intensity
and shape after the interaction with a target molecule.
The CPL signal accompanies total luminescence and provides
additional information, since the shape and signature of the CPL
spectrum is very sensitive to the coordination environment and
thus the signal may be very specific for a certain target.
Parker et al. reported Tb3+ and Eu3+ enantiopure cyclen-
Scheme 5. 2,6-Pyridine-dicarboxylate (L18) and chelidamic acid (L19).
based systems as CPL probes for proteins:9 Fig. 5 shows
the Tb3+ macrocyclic complex TbL21 employed for serum al-
bumin sensing.58
relationship (Pfeiffer effect).55,56 This event is signaled by the The complex bears three asymmetric carbon atoms on the
rising of an induced CPL signal in the region of the side-arms and it exists as a diastereomer pair: SSS-Δ-[TbL21]
5
D4 → 7 F5 transition. and SSS-Λ-[TbL21] with the former prevailing in solution.
With a similar approach, Parker et al. synthesized a cyclen- Serum albumin binds to SSS-Δ-[TbL21] (and only more
based Eu3+ (EuL20) complex in which the chirality of the com- weakly to its enantiomer), and as a consequence to the forma-
plex is defined by the position of the azaxanthone and carbox- tion of this adduct, the preferred helicity of TbL21 is reversed
ylate pendant arms but it is dynamically racemic, and of from Δ to Λ and a switching of the CPL spectrum signature is
course no CPL can be detected (Fig. 4).50,57 observed.59

Fig. 4. Binding between the EuL20 and α1-AGP. On the right: CPL (blue navy and orange) and total luminescence (light blue and red) for free and bound forms
(reproduced from Ref. 50 with permission of The Royal Chemical Society).
Chirality DOI 10.1002/chir
 LANTHANIDE CIRCULARLY POLARIZED LUMINESCENCE

3+
Me Ph
According to Parker et al.,50 it is also possible that the coor-
dination changes the geometry around the lanthanide provid-
HN O ing a twist angle closer to the ideal one for static coupling
N mechanism (namely, 22.5°) (see section below).
N N N
O Ln
N N N ORIGIN OF STRONG CPL
N N
Me H Any chiroptical activity requires a nonvanishing rotational
O strength:
NH
Ph  
Me ^ jii ¼ I μij mji
R ij ¼ I½hij^μj j ih j jm (4)
SSS-Δ[TbL21] where μ ^ are the electric and magnetic dipole transition
^ and m
operators and I is the imaginary part of the following expres-
sion. In an emission process the energy of the initial state i is
higher than that of the final state j; in this case Eq. (4) gauges
CPL.
For a magnetic dipole-allowed electric dipole-forbidden tran-
sition, like an Ln-centered f-f transition, μij ≈ 0 is expected and
therefore a vanishing rotational strength. The process giving rise
to CPL activity can be conveniently represented with reference to
two limiting mechanisms: static and dynamic coupling.22 The for-
mer is only possibly relevant when the ligand lacks any signifi-
cant chromophoric group; in all the other cases both
mechanisms should be taken carefully into account.

Static Coupling
Fig. 5. Lanthanide macrocyclic complex (TbL21) and CPL spectrum before In a dissymmetric environment, a mixing of, e.g., 4f and
(blue) and after (purple) addition of serum albumin (reproduced with permis-
sion from Ref. 9. Copyright 2009 American Chemical Society). 5d orbitals may provide the necessary odd-parity
interconfigurational character yielding μij ≠ 0.22,61 This can
This switching occurs selectively with serum albumin, happen only if the first coordination sphere is chiral and there-
while it does not with other proteins, cyclodextrins, or chiral fore the covalent contribution to the bonds between the lan-
anions. This led Parker and colleagues to envisage a potential thanide and the donor atoms entails invoking such hybrids.
use for these complexes as a probe for CPL microscopy.9 In the typical parlance of chiroptical spectroscopies, and in
The sensitive nature of the lanthanide-centered CPL has particular in ECD, this case can be described as an intrinsi-
been further demonstrated by Yuasa et al.8 A 1-biphenyl-3- cally chiral chromophore.
perfluoroethyldiketonate moiety was covalently bound to bo- In the limit of low covalence, the coordination neighbor-
vine serum albumin or other proteins, such as Staphylococcus hood causes only a weak perturbation of the metal states, so
aureus recombinant nuclease A and insulin. This diketonate the sum rule can apply, yielding a vanishing integral of the
has a strong affinity for lanthanides and is a good sensitizer CD or CPL spectrum over all the f transitions. This is hardly
for Eu3+; in fact, complexing these systems with Eu3+, the pro- of practical aid when we deal with a complex of Eu3+, Tb3+
tein fills the coordination sphere around the lanthanide as a or other visible-emissive lanthanides, because their transi-
function of its structural and chemical characteristics; in addi- tions range from the IR to UV region and many of them will
tion, it provides an asymmetric environment allowing one to almost surely be covered by ligand-centered bands.
record different Eu3+-centered CPL spectra (Fig. 6). Yb3+ and Ce3+ represent a special case: since they have a 4f1
and 4f13 electronic configuration, respectively, they behave
as monoelectronic systems with only two levels each. In
Lanthanide CPL and Ion Binding particular, while the Ce3+ 2 F7/2 → 2 F5/2 transition falls in
Lanthanides display strong affinity for hard anions, which the IR region and may be covered by ligand VCD signals,
are able to displace weak neutral ligands. Moreover, it is pos- Yb3+ 2 F7/2 → 2 F5/2 falls in the NIR region and can thus be
sible to tune the coordination strength of acidic ligands as a often easily recorded without significant interferences.32,62
function of pH and the pKa of the ligand itself. A variable coor- In the limit of perfect static coupling the integral over the
dination may modulate the coordination geometry to which manifold corresponding to the MJ splitting allied with this
CPL is sensitive. transition is expected to vanish.
Eu3+ complexes have been used as probes for bicarbonate or This result can be transferred to isostructural complexes of
pH.50,60 Various enantiopure cyclen-based structures have other lanthanides. Lanthanide complexes often show
been developed as responsive systems in which the concentra- isostructurality along the series; this means that the geome-
tion of bicarbonate can be tracked following the variation of the try of the system may show no significant dependence on
luminescence dissymmetry factor for a selected transition. the lanthanide ion.||
Complex EuL23, bearing a sulfonamide moiety on one arm,
||
has proven to be pH-responsive: when pH increases the sul- Ligand-centred ECD spectra of isostructural compounds do not display
fonamide moiety is deprotonated and thus it is able to coordi- significant variations. A nonchirooptical method to asses isostructurality
is through analysis of the NMR data; in fact, paramagnetic shifts and re-
nate the metal center; this results in a rigidification of the laxation rates of paramagnetic Ln3+ compounds contain geometric infor-
complex leading to increasing glum values at 632 nm (Fig. 7). mation. For details we refer to the specific literature.62,63
Chirality DOI 10.1002/chir
 ZINNA AND DI BARI

Fig. 6. Covalent binding of 1-biphenyl-3-perfluoroethyldiketonate to the protein and complexation with Eu3+ and Eu-centred CPL of various adducts (reproduced
from Ref. 8 with permission of The Royal Chemical Society).

For this mechanism, in the common case of a distorted with pure magnetic dipole character. Once more, making ref-
square antiprismatic geometry, as found for example in erence to common nomenclature in ECD theory, we deal with
DOTA-like complexes or in tetrakis diketonates (notably in an intrinsically achiral chromophore. Optical activity can stem
the case of CsEuL64), the CPL signal should vary with the twist from some coupling interaction between metal-centered tran-
angle ϕ following a sin(4ϕ) trend, so the maximum is reached sitions and the dissymmetric environment provided by the
for ϕ = 22.5° (Fig. 8).64 ligands beyond the first coordination sphere.
The previously cited CsEu(hfbc)4 (Scheme 3) complex pro-
Dynamic Coupling vides an interesting example to analyze.
When the coordination polyhedron is itself achiral, the li- CsEu(hfbc)4 has an almost perfect antiprismatic geometry
gand field should allow only for f → f electronic transitions in solution with a twist angle of
41.4°, thus static coupling
Chirality DOI 10.1002/chir
 LANTHANIDE CIRCULARLY POLARIZED LUMINESCENCE

Fig. 7. Top: changes in the coordination sphere of EuL23 as a response to increasing pH. Bottom: glum for the transition at 632 nm as a function of pH (reproduced
from Ref. 50 with permission of The Royal Chemical Society).

Fig. 9. Dynamic coupling mechanism occurring in a C4–symmetric Ln

Fig. 8. Twist angle ϕ in the case of a distorted square antiprismatic geometry. diketonate: for simplicity, only two β-diketonate moieties are depicted. The
four lobes represent the quadrupolar charge distribution (blue and yellow) al-
lied to the magnetic dipole transition (with moment mLn, along the y-axis).
This induces a polarization of the diketonate group, which is represented by
mechanism alone cannot account for the measured glum = 1.38 the two skew μlig vectors. The horizontal components of μlig provide nonvan-
value at 598 nm,65 i.e., for the 5D0 → 7 F1 transition, which has ishing terms to the scalar product m · μ. (Adapted from Ref. 67.)
magnetic dipole but no electric dipole character. Indeed, in an
ideal antiprismatic geometry the twist angle is 45°, which nearby diketonate groups constitute polarizable linear oscilla-
means that the coordination polyhedron is completely symmet- tors (μlig), which can be excited (through dipole–quadrupole
ric with respect to rotoreflection operations. interaction) when the 5D0 → 7 F1 transition is active, providing
On the other hand, dynamic coupling between the Eu- a m-μ coupling mechanism.66
centered and the nearby diketonate π → π* transitions may With reference to Fig. 9, the lanthanide-centered magnetic
help us rationalize this case. moment mLn (belonging to irrep E of the C4 point group) is
Fig. 9 represents two of the 4 β-diketonate moieties of the contained in the x–y plane, orthogonal to the C4 (z-axis).
CsEu(hfbc)4 complex (belonging to C4 point group). For the sake of simplicity, in Fig. 9 we represented only its
The lanthanide-centered 5D0 → 7 F1 magnetic transition y-component. The associated quadrupolar charge distribution
(mLn) is associated with electric quadrupole moment; the during this Ln-centered transition is shown as well.
Chirality DOI 10.1002/chir
 ZINNA AND DI BARI

Each diketonate can be depicted as a linear polarizable fluorescence experiment. On the other hand, if it were an issue,
group, directed parallel to the vector joining the two oxygen their large Stokes shift would allow one to adopt an in-line ge-
atoms; that is, oblique with respect to the x–y-plane. When ometry. To this end, one must prevent the exciter beam to
the Ln-centered transition is excited (either in absorption or reach the detector, which may be achieved by simply adding
in emission), its associated electric quadrupole induces a si- a lowpass filter after the sample. When using a diffraction-grate
multaneous electric dipole moment μlig on each diketonate. monochromator, one must be aware that higher harmonics of
In turn, these four electric dipoles couple with one another the exciting radiation may fall in the emission region.**
providing components with different symmetry: either be- Moreover, the large luminescence dissymmetry factors
longing to A-irrep, i.e., oriented along z, or doubly degenerate usually obtained for lanthanides may allow one to measure
(E) in the x-y plane. lanthanide CPL spectra using simple static optics, employing
Only this latter (low-energy) E component of the μlig -μlig a quarter wave retarder and a linear polarizer. Early measure-
coupling (μDyn.Coup) can constructively interact with the mLn ments in the field of CPL were made with similar devices
to provide rotational strength (consisting in the scalar prod- without photoelastic modulators, which are now common in
uct m · μ). On the contrary, the axial A-counterpart leads to CPL spectrophotometers.68
cancellation. This setup allowed Oosterhoof et al. to measure glum values
The dynamic coupling mechanism can only be efficient with a standard deviation within 0.005 and 0.01.69–71
when the lanthanide and the chromophoric group are spa-
tially close, since the dipole–quadrupole interaction depends
on the Ln-μlig distance R
4; moreover, it depends on the dif- More About the Luminescence Dissymmetry Factor
ference between the frequencies of the lanthanide-centered Plotting glum vs. λ. In a CPL measurement, ΔI and I are not ab-
and the ligand-centered transitions; this dependence can be solute quantities; in fact, as in ordinary fluorescence experi-
accounted for as a perturbation. When these conditions are ments, not all of the emitted light is detected, depending on
fulfilled, this mechanism can provide transitions with a strong the experimental conditions. On the other hand, the lumines-
circular polarization, if compared with the simple static cence dissymmetry factor, as defined in Eq. (1), is an absolute
coupling; in fact, dynamic coupling does not entail invoking value. Therefore, there are good physical reasons to discuss
Ln orbital hybridization, which is generally small, since the and report CPL spectra in terms of glum, not only of individ-
covalency is low in the Ln-ligand bond. ual bands but also as a continuous function of wavelength
When this mechanism is active, f → f transitions can no lon- (or wavenumber).
ger be considered isolated, because it is naturally coupled However, some precautions should be taken when plotting
with ligand-centered transition(s); so, unlike the case of static glum (λ).
coupling, the integral over the bands of the NIR-CD spectrum Indeed, out of the emission zones, I and ΔI are equal
of an Yb3+ isostructural complex will be nonvanishing. to 0, thus glum gives rise to a mathematically undefined
form: the practical result is an amplification of the instru-
mental fluctuations around zero,†† with erratic and possi-
SUGGESTIONS ON HOW TO MEASURE AND REPORT bly very large values of glum, where one would actually
CPL SPECTRA OF LANTHANIDE COMPLEXES expect 0. This may be quite a serious issue with lantha-
CPL spectra are measured through a continuous wave scan nides, since the emission bands are very narrow and com-
whose most significant parameters are the passing band w, monly without relevant tailing. Moreover, such narrow
the time constant k, and the scan speed v; they all display crit- bands are commonly instrumentally traced with very few
ical aspects when dealing with Ln complexes. data points; therefore, trying to eliminate the noise through
A general rule among spectroscopists states that these pa- smoothing algorithms is a risky choice; in fact, in this
rameters must fulfill the condition: way a faithful reproduction of the profile of these bands
can be hard to achieve.
1 We therefore suggest introducing a trivial mathematical ar-
w > kv (5)
2 tifice defining a corrected glum as:
Particular caution should be taken in setting the passing
ΔI
bandwidth; in fact, as stated above, lanthanide emission e
g lum ¼ (6)
bands can be very narrow (less than 5 nm), and they are often I þδ
multiplets with nearby bands, with possibly opposite CPL where the correcting constant δ has to be chosen bigger than
sign; if these components remain unresolved, they will cancel the instrumental noise but negligible with respect to the
out (at least partially), causing error in the assessment of the smallest emission signal one wants to measure (for example,
intensity of the CPL signal and in the calculation of the glum 1/100 of I).
value. As an example, in Fig. 10 we show a plot of glum (without
With a passing band of 1 nm and a time constant of 1 sec, correction) and eg 1um (δ = 3 · 10
4, i.e., 2/100 of the maximum
the scan speed should be set to 0.5 nm/sec. As an example, intensity of the band at 585 nm) for a CPL spectrum obtained
we note that it will take 4 min for each scan to acquire a for CsEu(hfbc)4.
120-nm region: this may be typical when dealing with Eu3+ For instance, considering the 550–570 nm region, one can
complexes. see that the correction is sufficient to smooth the baseline
A low enough scan speed is also necessary to accurately de-
tect the emission maxima of the narrow CPL lines, which in
**For example, setting the excitation to 305 nm may interfere with the
turn is necessary to calculate accurate glum values. 610 nm band of an Eu3+ complex.
Lanthanide CPL spectra are usually recorded with a 90° ge- ††
This noise comes from the definition of glum itself and not directly from
ometry between the source and the detector, as in an ordinary the experimental measurement.
Chirality DOI 10.1002/chir
 LANTHANIDE CIRCULARLY POLARIZED LUMINESCENCE

• form a complex with a chiral geometry that can give

rise to a strong CPL, according to the mechanisms de-
scribed herein;
• form a complex with good solubility in the intended sol-
vent or medium.

Lanthanide peculiar spectroscopic features (large Stokes

shift, narrow and characteristic emission bands), joined with
their outstanding circularly luminescence properties, can
give rise to a multidisciplinary interest. The selectivity of the
CPL response is employed as a bioanalytical method to quan-
tify and track biomarkers, and more specific tools, such as cir-
cularly polarized microscopy, can be developed using tailored
lanthanide complexes.1,9
Other applications, in which luminescent lanthanide com-
plexes are already employed, can be extended using chiral
Fig. 10. Plot of glum with (red) and without correction (black) for analogs with strong circularly polarized emission; this may in-
CsEu(hfbc)4. Notice that the baseline is smoothed while the bands are not
affected by the correction (insets). The CPL and emission spectra for generating clude, for example, the development of electroluminescent
this plot were recorded on the instrument described in Ref. 68. circularly polarized light emitters.
Another asset worth employing is the luminescence of dif-
ferent lanthanides extending to the near-infrared (NIR) re-
while not large enough to significantly affect the signal bands gion; this would allow one to obtain molecules with
(Insets of Fig. 10). circularly polarized emission in a region that cannot be easily
Instrumental Error on glum. Since the pulses due to incident reached with chiral organic emitters. However, so far, only
light on the detectorpfollow Poisson statistics, the associate few pioneering works concerning the measurement of CPL
ffiffiffiffi in the NIR region have been reported,72–74 and therefore it re-
standard deviation is N , where N is the total number of pho-
mains a relatively novel field to explore.
ton counts. The standard deviation on ΔI = q IL

ffiffiffiffiffiIR is σ ΔI ¼
pffiffiffiffiffiffiffi
2N , while on I = 1/2(IL + IR), it is σ I τoτ ¼ N2 : To derive ACKNOWLEDGMENTS
the standard deviation σ g on glum, we have to solve:‡‡ Financial support from MIUR-PRIN 2012A4Z2RY is gratefully
1um
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi acknowledged. We thank Profs. S. Abbate and G. Longhi and
   
∂g lum 2 2 ∂g lum 2 2 Dr. E. Castiglioni for recording the spectra of CsEu(hfbc)4.
σ g lum ¼ σ ΔI þ σI (7)
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Chirality DOI 10.1002/chir