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DOI: 10.1039/B913902H (Paper) Dalton Trans. , 2009, 8421-8425

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Sensitised near-IR lanthanide luminescence exploiting anthraquinone-derived

chromophores : syntheses and spectroscopic properties

Jennifer E. Jones and Simon J. A. Pope*

School of Chemistry, Main Building, Cardiff University, Cardiff, CF10 3AT, Cymru/Wales, UK. E-mail:
[email protected] ; Fax: +44 2920874030; Tel: +44 2920879316

Received 13th July 2009, Accepted 18th August 2009

First published on 2nd September 2009

Abstract
The syntheses of two anthraquinone-derived tetraaza macrocyclic ligands (L1via 1-amino-
9,10-anthraquinone and L2via 1-amino-4-hydroxy-9,10-anthraquinone ) together with their
corresponding LnIII complexes, Ln-L1/2 (Ln = NdIII, GdIII, ErIII, YbIII), are described. Both Ln-L1

(λmax≈ 380 nm) and Ln-L2 (λmax≈ 450 nm) complexes absorb in the visible region with good
extinction coefficients (εvis > 2 × 103 M−1 cm−1). Phosphorescence measurements on Gd-L1/2 at
77 K allowed the ligand-centred triplet states to be estimated at ca. 22000 cm−1 and 19800 cm−1

for Gd-L1 and Gd-L2 respectively. Steady state and time-resolved measurements showed that
both chromophores sensitised NdIII, ErIII and YbIII ions, resulting in observable near-IR
emission. Preliminary studies on the pH-dependent behaviour of the L2 derivatives
demonstrated that deprotonation of the 4-hydroxyl group at pH 12 resulted in a significant
 bathochromic shift in the absorption profile, thus allowing sensitised near-IR emission utilising
λex = 575 nm.

Introduction

Near-IR emitting lanthanides such as NdIII, ErIII and YbIII luminesce from f-centred excited states.
Therefore, one of the challenges for the synthetic chemist is the design and use of a sensitising
chromophore which overcomes the formally forbidden nature of the f → f transition. 1 From an
energetic standpoint it is logical to utilise chromophoric entities that absorb into the visible region,
thus allowing effective population of the NdIII, ErIII and YbIII emitting states. This is particularly

appropriate when considering applications in the field of fluorescence imaging microscopy where
high energy excitation and emission should be avoided to minimise tissue or cell damage, and to
enhance image quality by reducing endogenous autofluorescence. 2 Synthetic approaches can be

employed to address such issues: firstly, the exploitation of organic chromophores (polyaromatics, 3
heterocycles, 4 functionalised aromatics 5 ) and, secondly, the development of sensitising d-block

transition metal entities. 6 The latter area often yields chromophores with excellent (and tunable)

molar absorption in the visible region (particularly the d6-based systems RuII, ReI, OsII and IrIII which
possess charge transfer bands), with numerous opportunities for tuning the physical and optical
characteristics via step-wise addition of functionalised ligands to the d-metal ion of choice. 6 However,
the covalent construction of the corresponding mixed d–f species is often synthetically non-trivial.
Simple anthraquinone dyes can also possess high molar extinction coefficients in the visible
region. They have been exploited as textile colourants and within synthetic polymers , 7 as well as
having biological and pharmaceutical importance (particularly with respect to antibiotics and
antitumour activity). 8 Specifically, the hydroxy-anthraquinone unit has been identified as the

biologically active site within anthracycline -based antitumour therapeutics, and is also naturally
occurring and extractable from selected plant life. 9 Interestingly anthraquinone -tethered platinum

complexes have been shown to accumulate in cancer cell spheroids (useful models for tumours),
demonstrating improved cellular accumulation over cisplatin. 10

Despite their favourable optical properties, anthraquinone derivatives have not been fully
exploited as photoactive chromophoric components within lanthanide-based architectures and the
scope appears limited to a recent report on the optical properties of EuIII-doped thin films incorporating

hydroxyanthraquinones. 11 Generally, their use as photoactive components (and more specifically as

electron acceptors 12 ) within supramolecular chemistry has been more extensively investigated 13
and can be exploited in the use of responsive chemosensors. 14

Within this paper we describe the chemistry associated with synthesising anthraquinone -
appended ligand architectures ( Scheme 1 ), appropriate for yielding water soluble, kinetically inert
lanthanide complexes, together with the resultant photophysical attributes of the complexes.

Scheme 1 Synthesis of the ligands and corresponding complexes: (i) 1 or 2, KI, iPr2EtN, PhMe, Δ; (ii)
TFA, DCM ; (iii) Ln(OTf)3, MeOH.

Synthesis

The synthetic development of commercially available 1-amino-9,10-anthraquinone (R = H ) and

1-amino-4-hydroxy-9,10-anthraquinone (R = OH) relies upon conversion to the corresponding
chloroacetamides 3b 1 and 2 prior to covalent attachment to the tert-butyl triester derivative of

cyclen. 4b Although this reaction was relatively slow (the nucleophilicity of the amine is deactivated by
the electron-withdrawing anthraquinone unit and the amine is sterically hindered) the use of excess
chloroacetyl chloride led to good yields. Importantly, if base was added stoichiometrically, such
conditions did not result in esterification where R = OH. Alkylation of the triester derivative of cyclen
did not occur under standard conditions: 4b reaction in MeCN or DMF in the presence of NaHCO3 or

organic bases over the course of 48 h resulted only in retrieval of starting materials. A successful
alternative was to heat the reactants in toluene , in the presence of iPr2EtN and stoichiometric KI over
the course of 24 h. These conditions usually resulted in complete conversion to the desired tetra-
alkylated cyclen derivatives E1 (R = H ) and E2 (R = OH), usually without need for further
purification . If required, removal of excess unreacted chromophore was achieved using silica
column chromatography , with elution with CH2Cl2. These precursors were characterised using 1H,
13C{1H} NMR , IR , ES MS and UV-vis spectroscopy . The corresponding free ligands were obtained
with standard deprotection ( tert-butyl cleavage) conditions (TFA, DCM ; 50/50) liberating the triacids,
L1 (R = H ) and L2 (R = OH). Reaction with Ln(OTf)3 gave the monometallic complexes.

Spectroscopic properties of the ligands and complexes

Firstly, an investigation of the UV-vis properties of the free ligands revealed that the hydroxy-
derivative, L2, possessed lower energy absorption bands in comparison to L1 (see Fig. 1 ). The visible
absorption bands were associated with favourable extinction coefficients of ca. 4 × 103 M−1 cm−1 for L1

and L2 in water , and comparable with related functionalised amino-anthraquinones. 15 These were
assigned as a ligand-centred 1ππ* transition. Previous studies (both experimental 16 and
theoretical 17 ) have shown that this band is composed of significant charge transfer character (an

intramolecular charge transfer: ICT), originating from a HOMO (dominant amine character) to LUMO
(large quinone component) electronic transition. This was evidenced by the observation that
reducing the electron donating ability of the amine (i.e. conversion of the free amines to the
corresponding acetamide derivatives 1 and 2) resulted in a blue-shift in the lowest energy absorption
band. 16a Previous reports into related hydroxyanthraquinones have shown that the pK of the –OH
a

group is largely determined by its position on the aromatic ring: positions 1 and 4 increase the pKa to

approximately 9 due to intramolecular hydrogen -bonding with the quinone oxygen. 18 As a

consequence deprotonation of L2 at pH 12 resulted in a shift of the lowest energy absorption to 550–
650 nm, which also revealed a vibronic structure suggesting more effective vibronic coupling thoughout
the chromophore as a result of enhanced aromaticity and rigidity. 16b,c The absorption properties of
the corresponding lanthanide complexes were dominated by the anthraquinone components, with
only minor deviations observed when compared to the free ligands (i.e. for Ln-L1λabsca. 380 nm; for Ln-
L2, λabsca. 450 nm).
Fig. 1 UV-vis absorption spectra recorded in aqueous solution using approximately 10−4 M

solutions.

Fig. 2 Steady state emission spectra for Ln-L2 (black, Yb; grey, Nd; light grey, Er) measured in D2O

using λex = 450 nm. Spectra offset for clarity.

 Fig. 3 pH dependent emission from Yb-L2 in D2O using λex = 575 nm and (inset) corresponding
absorption spectrum (grey, pD 7; black, pD 12).

The free ligands were luminescent in aqueous solution at room temperature. L1 was emissive at ca.
500 nm (λex = 380 nm), whilst L2 possessed a broad emission at ca. 575 nm (λex = 450 nm); both are
assigned to a fluorescence (τL1 < 1 ns; τL2 = 1.1 ns) originating from the CT-dominated 1ππ* transition,

although due to the insolubility of these species in non-polar media, the solvatochromic behaviour was
not investigated. The triplet excited state (3ππ*) energy of each chromophore was estimated from the
onset of the spectral profile of a time-gated (0.5 ms) phosphorescence spectrum , obtained at 77 K,
from an ethanol glass of Gd-L1/2. For Gd-L1 this value was approximately 22000 cm−1 and for the
hydroxy analogue this phosphorescence was shifted to 19800 cm−1. These observations suggest that
both chromophores should adequately sensitise the accepting excited states of NdIII, ErIII and YbIII.
Following irradiation of the chromophores (λex = 380 nm for Ln-L1; λex = 450 nm for Ln-L2), each of

the complexes displayed dual emission: visible emission associated with residual anthraquinone -
based fluorescence and characteristic lanthanide-based luminescence in the near-IR region ( Fig. 2 ).
Specifically, the NdIII complex displayed near-IR emission dominated by a peak at 1058 nm (4F3/2→4I11/2)
with a weaker feature at ca. 1340 nm, corresponding to 4F3/2→4I13/2. The steady state emission spectra
of Yb-L1/L2 gave spectral profiles typical of YbIII with a structured peak at 975 nm (2F5/2→2F7/2). Er-L1/L2
also gave broad emission features centred around 1540 nm and assigned to the 4I13/2→3H4 transition.
Luminescence lifetimes ( Table 1 ) were also obtained on H2O/D2O solutions and were single
exponential in every case, at the wavelength of detection. The measured lifetimes of NdIII and YbIII can

be utilised to deduce the inner sphere coordination environment, in terms of the degree of lanthanide
hydration, q [q = A{(kH O− kD O) − B}; for YbIII A = 1 μs, B = 0.2 μs−1; for aqueous NdIIIq = 130(kH O− kD O) −
2 2 2 2

0.4]. 19 These values were consistent with the incorporation of the lanthanide ions into an eight-
coordinate binding site of the ligands. The values also compare favourably with closely related
aminocarboxylate ligands based upon the mono-amide functionalised DO3A core. 3b,5a Lifetime
decays for Er-L1/L2 were only obtainable in D2O due to the poor emissivity of ErIII in non-deuterated
media. 1,3c

Table 1 Visible absorbance and near-IR photophysical data

Compound λabs/nm τ (H2O)/ns a τ (D2O)/ns a q

Nd-L1 b 379 96 377 0.6
Er-L1 c 379 — 870 —
Yb-L1 d 379 747 6818 1
Nd-L2 b 449 88 295 0.6
Er-L2 c 453 — 1056 —
Yb-L2 d 449 836 6861 0.9

a λex = 355 nm. b λem = 1060 nm. c λem = 1535 nm. d λem = 975 nm.

Given the notable red-shift in the absorption profile of L2 at pH 10 or above, a solution of Yb-L2 at
pH 7 was irradiated with 575 nm light to give a featureless spectrum with no evidence for YbIII-based
emission. The solution was then basified to pH 12, resulting in a deep purple coloured solution, with
the resultant steady state spectrum showing the characteristic 2F5/2→4F7/2 transition ( Fig. 3 ). These

results suggest that the advantageous chromophoric properties of the functionalised anthraquinones
can be further enhanced by simple pH modulation.

Conclusions

This paper presents the use of functionalised 1-amino-anthraquinones for use as sensitising
chomophores in lanthanide complexes. Although conversion to the chloroacetamides 1 and 2 was
possible using standard synthetic conditions, their corresponding use as alkylating agents required
more forcing conditions, which ultimately gave the pro-ligands E1 and E2 in excellent yields. The
resultant lanthanide complexes possessed excellent absorption characteristics with the hydroxy -
based species Ln-L2 demonstrating especially favourable properties that can be further enhanced via
pH modulation. Both chromophores facilitated sensitised near-IR LnIII emission, following excitation

in the visible region. Again, those complexes based upon L2 allowed longer wavelength excitation (ca.
440–460 nm). In summary, the extremely favourable chromophoric attributes of
aminoanthraquinone derivatives recommend them as valuable alternatives in the ongoing
development of lanthanide-based luminescent complexes. We are currently investigating the biological
implications of such complexes with a view to elucidating DNA binding , cellular accumulation and
intracellular distribution.

Experimental

Materials and procedures

1-Amino-9,10-anthraquinone and 1-amino-4-hydroxy-9,10-anthraquinone were purchased from

Aldrich Chemical Company. Although all new compounds are air stable both in the solid state and
solution, the free ligands and complexes are mildly hygroscopic if left to the open atmosphere for
prolonged periods. pH titrations were carried out in a background of constant ionic strength (I = 0.1
NaCl, 295 K). Solutions were made basic by addition of 1 M NaOH and titrated to acidic pH using small
aliquots of (1–30 μL) of 1 M, 0.1 M or 0.01 M HCl solution in accordance with related studies. In order to
avoid any errors due to dilution, HCl solutions contained the same concentration of complex as the
sample.

General physical measurements

All photophysical data were obtained on a JobinYvon-Horiba Fluorolog spectrometer fitted with a JY
TBX picosecond photodetection module and a Hamamatsu R5509-73 detector (cooled to −80 °C using
a C9940 housing) for near-IR measurements. For the near-IR lifetimes the pulsed laser source was a
Continuum Minilite Nd:YAG configured for 355 nm output. For the fluorescence lifetimes 372 and 459
nm NanoLEDs (operating at 1 MHz) were utilised. All lifetimes were obtained using the JY-Horiba
FluoroHub single photon counting module. IR spectra were recorded on an ATR equipped Varian
7000 FT-IR . LR mass spectra were obtained using a Bruker MicroTOF LC . UV-vis data were
recorded as solutions on a Jasco 570 spectrophotometer .

Syntheses of precursors, ligands and corresponding lanthanide complexes

Synthesis of 1. Chloroacetylchloride (0.32 ml, 37.6 mmol)) in MeCN (5 ml) was added dropwise
to a solution of 1-amino-9,10-anthraquinone (500 mg, 22.4 mmol) and triethylamine (0.34 ml, 24.4
mmol) in MeCN (5 ml) at 0 °C. The reaction was allowed to reach room temperature and after 48 h,
solvent removed in vacuo, CH2Cl2 added and washed with water (2 × 25 ml). The organic phase was
collected, dried, filtered and solvent removed in vacuo, yielding a yellow powder (0.413 g, 64%). 1H

NMR (400 MHz, CDCl3) δH = 9.05 (dd, 3JHH = 8 Hz, 1H, ArH), 8.30 (m, 1H, ArH), 8.20 (m, 1H, ArH), 8.10 (dd,
3J
HH = 8 Hz, 1H, ArH), 7.75 (m, 3H, ArH), 4.20 (s, 2H, CH2) ppm. EI MS found m/z = 299 {M}+.
 Synthesis of 2. Chloroacetylchloride (0.3 ml, 40.3 mmol) in MeCN (5 ml) was added dropwise to
a solution of 1-amino-4-hydroxy-9,10-anthraquinone (500 mg, 20.9 mmol) and triethylamine (0.32
ml, 20.9 mmol) in MeCN (5 ml) at 0 °C. The reaction was allowed to reach room temperature and, after
48 h, solvent removed in vacuo, CH2Cl2 added and washed with water (2 × 25 ml). The organic phase
was collected, dried, filtered and solvent removed in vacuo, yielding a red powder (0.550 g, 66%). 1H
NMR (400 MHz, CDCl3) δH = 9.05 (d, 3JHH = 9.2 Hz, 1H, ArH), 8.25 (m, 2H, ArH), 7.75 (m, 2H, ArH), 7.35 (d,
3J
HH = 9.6 Hz, 1H, ArH), 4.23 (s, 2H, CH2) ppm. EI MS found m/z = 315 {M}+.
Synthesis of E1. Chloracetamide 1 (75 mg, 0.251 mmol), 1,4,7-tris(tert-
butoxycarbonylmethyl)-1,4,7,10-tetraazacyclododecane (150 mg, 0.252 mmol), KI (42 mg, 0.251
mmol) and EtNiPr2 (0.1 ml, excess) were added to toluene (10 ml) under inert conditions. The reaction
was heated at 90 °C for 5 h, the reaction monitored by TLC (CH2Cl2: MeOH, 9 : 1) until completion. The
reaction was allowed to cool before removal of the solvent in vacuo. Ethyl acetate was added,
washed with water (2 × 20 ml), dried over magnesium sulfate , filtered and removed in vacuo
yielding an orange oil (0.231 g, 97%). 1H NMR (400 MHz, CDCl3) δH = 9.20 (1H, d, ArH), 8.25 (2H, m, ArH),
8.05 (1H, d, ArH), 7.70 (3H, m, ArH), 3.38 (2H, s, -CH2-CON), 3.27 (4H, s, -CH2-COOBu), 3.23 (2H, s, -CH2-
COOBu), 3.0 (4H, m, ring), 2.89 (8H, m, ring), 2.80 (4H, m, ring) 1.39 (9H, s, tert-Bu), 1.33 (18H, s, tert-Bu)
ppm. 13C{1H} NMR (101 MHz, CDCl3) δC = 186.5, 181.4, 172.0, 171.9, 171.0 (all CO),140.3, 134.3, 133.9,

133.7, 133.1, 132.8, 131.7, 126.5, 125.1, 121.8, 117.0, 116.8, 80.9, 57.1, 54.8, 51-49 (br), 39.6, 27.2, 26.9
ppm. ES+ MS found m/z = 800 {M + Na}+.
Synthesis of E2. Chloracetamide 2 (53 mg, 0.168 mmol), 1,4,7-tris(tert-
butoxycarbonylmethyl)-1,4,7,10-tetraazacyclododecane (100 mg, 0.168 mmol), KI (27 mg, 0.168
mmol) and EtNiPr2 (0.1 ml, excess) were added to toluene (10 ml) under inert conditions. The reaction
was heated at 90 °C for 8 h, the reaction monitored by TLC ( DCM –MeOH, 9 : 1) until completion. The
reaction was allowed to cool before removal of the solvent in vacuo. Ethyl acetate was added,
washed with water (2 × 20 ml), dried over magnesium sulfate , filtered and removed in vacuo
yielding a red oil (0.105 g, 77.%). 1H NMR (400 MHz, CDCl3) δH = 9.15 (1H, d, ArH), 8.27 (2H, m, ArH),
7.75 (2H, m, ArH), 7.29 (1H, d, ArH), 3.37 (2H, s, -CH2-CON), 3.27 (4H, s, -CH2-COOBu), 3.20 (2H, s, -CH2-
COOBu), 3.0 (4H, m, ring), 2.89 (8H, m, ring), 2.80 (4H, m, ring) 1.40 (9H, s, tert-Bu), 1.34 (18H, s, tert-Bu)
ppm. 13C{1H} NMR (101 MHz, CDCl3) δC = 187.3, 183.2, 171.5, 170.3, 170.0, 158.7, 134.6, 133.7, 133.4,
133.0, 131.5, 130.2, 126.5, 125.9, 125.6, 115.8, 113.3, 79.8, 55.6, 53.1, 51.7, 51.5, 51.2, 51.1, 27.3, 27.2
ppm. ES+ MS found m/z = 794 {M + H}+, 816 {M + Na}+.
Synthesis of L2 and L1. E2 was dissolved in CH2Cl2 (3 ml) and trifluoroacetic acid (3 ml) added
dropwise. The reaction was stirred at room temperature for 48 h. The solvents were removed in
vacuo, and the residue repeatedly redissolved in methanol and dried under reduced pressure (×4).
The resultant residue was dissolved in a minimum volume of ethanol and added dropwise to stirring
diethyl ether at 0 °C, producing L2 a red precipitate (63 mg, 84%). 1H NMR (400 MHz, D2O) δH = 8.15
(1H, d, 3JHH = 9.6 Hz, ArH), 7.50 (4H, m, ArH), 6.80 (1H, d, 3JHH = 9.6 Hz, ArH), 4.1-2.8 (24H, br m, -CH2-)

ppm. ES+ MS found m/z = 688 {M+Zn2+-H+}+. HRMS ( ES+ ) found m/z 626.2451 {M + H}+; C30H36N5O10
requires 626.2457. UV-vis . λmax (ε/mol−1 dm3 cm−1): 370 (1600), 464 (6700) nm.
The same procedure was followed for the deprotection of E1 but left for 72 h, yielding L1 a yellow
precipitate as a first crop (47 mg, 23%). Further crops were obtained by storing the ethanol /ether
solution in a fridge freezer. 1H NMR (400 MHz, D2O) δH 8.25 (1H, bm, ArH), 7.6 (6H, br m, ArH), 3.8–3.0
(24H, m, -CH2-) ppm. ES+ MS found m/z = 672 {M + Zn2+− H+}+. HRMS ( ES+ ) found m/z 610.2491 {M +
H}+; C30H36N5O9 requires 610.2508. UV-vis . λmax (ε/mol−1 dm3 cm−1): 310 (3800), 398 (5500) nm.
General procedure for the formation of lanthanide complexes. A mixture of the ligand and
the appropriate Ln(OTf)3 was stirred in MeOH at 50 °C for 24 h. The solution was reduced in vacuo then
added dropwise to stirring diethyl ether at 0 °C. The precipitate was filtered, washed with diethyl
ether and dried in vacuo to give the desired lanthanide complex.
NdL1 was isolated as an orange powder. UV-vis . λmax (ε/mol−1 dm3 cm−1): 307 (2300), 379 (4400) nm.
IR νmax(solid): 1734, 1700, 1653, 1576 (C O) cm−1. ES+ MS : found m/z 751.1 {M + H}+ and 765.1 {M +
OH}+ HRMS ( ES+ ) found m/z 749.1347 {M + H}+; C30H33N5O9142Nd requires 749.1350.

GdL1 was isolated as an orange powder. UV-vis . λmax (ε/mol−1 dm3 cm−1): 305 (2000), 379 (4400) nm.
IR νmax(solid): 1720, 1701, 1666, 1659, 1577 (C O) cm−1. ES+ MS : m/z 765.2 {M + H}+. HRMS ( ES+ )
found m/z 761.1472 {M + H}+; C30H33N5O9154Gd requires 761.1481.
ErL1 was isolated as an orange powder. UV-vis . λmax (ε/mol−1 dm3 cm−1): 305 (2000), 379 nm (2800).
IR νmax(solid): 1717, 1700, 1669, 1658, 1577 (C O) cm−1. ES+ MS : m/z 775 {M + H}+. HRMS ( ES+ )
found m/z 795.1385 {M + Na}+; C30H32N5O9Na166Er requires 795.1395.

YbL1 was isolated as an orange powder. UV-vis . λmax (ε/mol−1 dm3 cm−1): 306 (2300), 379 (4600) nm.
IR νmax(solid): 1725, 1700, 1653, 1583 (C O) cm−1. ES+ MS : m/z 781.2 {M + H}+. HRMS ( ES+ ) found
m/z 799.1441 {M + Na}+; C30H32N5O9Na170Yb requires 799.1440.
NdL2 was isolated as a red powder. UV-vis . λmax (ε/mol−1 dm3 cm−1): 367 (1000), 449 (4100) nm. IR
νmax (solid): 1734, 1700, 1656, 1576 (C O) cm−1. ES+ MS : m/z 767.2 {M + H}+. HRMS ( ES+ ) found m/z
787.1111 {M + Na}+; C30H32N5O10142Nd requires 787.1119.

GdL2 was isolated as a red powder. UV-vis . λmax (ε/mol−1 dm3 cm−1): 368 (1800), 454 (6400) nm. IR
νmax (solid): 1734, 1700, 1635, 1578 (C O) cm−1. ES+ MS : m/z 781.1 {M + H}+. HRMS ( ES+ ) found m/z
778.1449 {M + H}+; C30H33N5O10155Gd requires 778.1448.
 ErL2 was isolated as a red powder. UV-vis . λmax (ε/mol−1 dm3 cm−1): 368 (1000), 453 (3500) nm. IR
νmax (solid): 1734, 1700, 1661, 1577 (C O) cm−1. HRMS ( ES+ ) found m/z 789.1525 {M + H}+;
C30H33N5O10166Er requires 789.1525.
YbL2 was isolated as a red powder. UV-vis . λmax (ε/mol−1 dm3 cm−1): 366 (1200), 449 (4100) nm. IR
νmax (solid): 1735, 1698, 1643, 1590 (C O) cm−1. ES+ MS : m/z 797.2 {M + H}+. HRMS ( ES+ ) found m/z
794.1584 {M + H}+; C30H33N5O10171Yb requires 794.1585.

Acknowledgements

The EPSRC are thanked for support (EP/E048390/1) together with Cardiff University. Dr Robert Jenkins,
Mr Robin Hicks and Mr David Walker are thanked for running low resolution mass spectra. The staff of
the EPSRC MS National Service at the University of Swansea are also gratefully acknowledged.

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