Inorganic Chemistry
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(56) Sørensen, T. J.; Faulkner, S. Multimetallic Lanthanide
Complexes: Using Kinetic Control To Define Complex Multimetallic
Arrays. Acc. Chem. Res. 2018, 51 (10), 2493−2501.
pediatric magnetic resonance imaging. Pediatr. Radiol. 2017, 47 (5),
507−521.
(73) Heffern, M. C.; Matosziuk, L. M.; Meade, T. J. Lanthanide
Probes for Bioresponsive Imaging. Chem. Rev. 2014, 114 (8), 4496−
4539.
(57) Heffern, M. C.; Matosziuk, L. M.; Meade, T. J. Lanthanide
probes for bioresponsive imaging. Chem. Rev. 2014, 114 (8), 4496−
539.
(74) Parker, D.; Dickins, R. S.; Puschmann, H.; Crossland, C.;
Howard, J. A. K. Being Excited by Lanthanide Coordination
Complexes: Aqua Species, Chirality, Excited-State Chemistry, and
Exchange Dynamics. Chem. Rev. 2002, 102 (6), 1977−2010.
(75) Peters, J. A.; Djanashvili, K.; Geraldes, C. F. G. C.; Platas-
iglesias, C., Structure, Dynamics, and Computational Studies of
Lanthanide-Based Contrast Agents. The Chemistry of Contrast Agents
in Medical Magnetic Resonance Imaging; John Wiley, 2001; pp 209−
276.
(58) Albin, M.; Horrocks, W. D.; Liotta, F. J. Characterization of a
potentially axially symmetric europium(III) complex of a tetraaceta-
te,tetraaza, macrocyclic ligand by luminescence excitation, emission
and lifetime spectroscopy. Chem. Phys. Lett. 1982, 85 (1), 61−64.
(59) Brittain, H. G.; Desreux, J. F. Luminescence and NMR studies
of the conformational isomers of lanthanide complexes with an
optically active polyaza polycarboxylic macrocycle. Inorg. Chem. 1984,
23 (26), 4459−4466.
(60) Aime, S.; Botta, M.; Ermondi, G. NMR study of solution
structures and dynamics of lanthanide(III) complexes of DOTA.
Inorg. Chem. 1992, 31 (21), 4291−4299.
(76) Drew, M. G. B. Structures of high coordination complexes.
Coord. Chem. Rev. 1977, 24 (2), 179−275.
(77) Parker, D.; Williams, J. A. G. Getting excited about lanthanide
complexation chemistry. J. Chem. Soc., Dalton Trans. 1996, No. 18,
3613−3628.
(61) Hoeft, S.; Roth, K. Struktur und Dynamik von Lanthanoid-
̈
Tetraazacyclododecantetraacetat-(DOTA-)Komplexen in Losung.
Chem. Ber. 1993, 126 (4), 869−873.
(78) Woods, M.; Payne, K. M.; Valente, E. J.; Kucera, B. E.; Young,
V. G. Crystal Structures of DOTMA Chelates from Ce3+ to Yb3+:
Evidence for a Continuum of Metal Ion Hydration States. Chem. -
Eur. J. 2019, 25 (42), 9997−10005.
(62) Aime, S.; Botta, M.; Fasano, M.; Marques, M. P. M.; Geraldes,
C. F. G. C.; Pubanz, D.; Merbach, A. E. Conformational and
Coordination Equilibria on DOTA Complexes of Lanthanide Metal
Ions in Aqueous Solution Studied by 1H-NMR Spectroscopy. Inorg.
Chem. 1997, 36 (10), 2059−2068.
(79) Woods, M.; Kovacs, Z.; Zhang, S.; Sherry, A. D. Towards the
Rational Design of Magnetic Resonance Imaging Contrast Agents:
Isolation of the Two Coordination Isomers of Lanthanide DOTA-
Type Complexes. Angew. Chem. 2003, 115 (47), 6069−6072.
(80) Ranganathan, R. S.; Raju, N.; Fan, H.; Zhang, X.; Tweedle, M.
F.; Desreux, J. F.; Jacques, V. Polymethylated DOTA Ligands. 2.
Synthesis of Rigidified Lanthanide Chelates and Studies on the Effect
of Alkyl Substitution on Conformational Mobility and Relaxivity.
Inorg. Chem. 2002, 41 (25), 6856−6866.
(81) Dai, L.; Jones, C. M.; Chan, W. T. K.; Pham, T. A.; Ling, X.;
Gale, E. M.; Rotile, N. J.; Tai, W. C.-S.; Anderson, C. J.; Caravan, P.;
Law, G.-L. Chiral DOTA chelators as an improved platform for
biomedical imaging and therapy applications. Nat. Commun. 2018, 9
(1), 857.
(82) Zhang, S.; Kovacs, Z.; Burgess, S.; Aime, S.; Terreno, E.; Sherry,
A. D. {DOTA-bis(amide)}lanthanide Complexes: NMR Evidence for
Differences in Water-Molecule Exchange Rates for Coordination
Isomers. Chem. - Eur. J. 2001, 7 (1), 288−296.
(83) Boros, E.; Srinivas, R.; Kim, H. K.; Raitsimring, A. M.;
Astashkin, A. V.; Poluektov, O. G.; Niklas, J.; Horning, A. D.; Tidor,
B.; Caravan, P. Intramolecular Hydrogen Bonding Restricts Gd−
Aqua-Ligand Dynamics. Angew. Chem., Int. Ed. 2017, 56 (20), 5603−
5606.
(63) Aime, S.; Barge, A.; Bruce, J. I.; Botta, M.; Howard, J. A. K.;
Moloney, J. M.; Parker, D.; de Sousa, A. S.; Woods, M. NMR,
Relaxometric, and Structural Studies of the Hydration and Exchange
Dynamics of Cationic Lanthanide Complexes of Macrocyclic
Tetraamide Ligands. J. Am. Chem. Soc. 1999, 121 (24), 5762−5771.
(64) Dunand, F. A.; Aime, S.; Merbach, A. E. First 17O NMR
Observation of Coordinated Water on Both Isomers of [Eu-
(DOTAM)(H2O)]3+: A Direct Access to Water Exchange and its
Role in the Isomerization1. J. Am. Chem. Soc. 2000, 122 (7), 1506−
1512.
(65) Woods, M.; Aime, S.; Botta, M.; Howard, J. A. K.; Moloney, J.
M.; Navet, M.; Parker, D.; Port, M.; Rousseaux, O. Correlation of
Water Exchange Rate with Isomeric Composition in Diastereoiso-
meric Gadolinium Complexes of Tetra(carboxyethyl)dota and
Related Macrocyclic Ligands. J. Am. Chem. Soc. 2000, 122 (40),
9781−9792.
(66) Dunand, F. A.; Dickins, R. S.; Parker, D.; Merbach, A. E.
Towards Rational Design of Fast Water-Exchanging Gd(dota-Like)
Contrast Agents? Importance of the M/m Ratio. Chem. - Eur. J. 2001,
7 (23), 5160−5167.
(67) Dickins, R. S.; Parker, D.; Bruce, J. I.; Tozer, D. J. Correlation
of optical and NMR spectral information with coordination variation
for axially symmetric macrocyclic Eu(iii) and Yb(iii) complexes: axial
donor polarisability determines ligand field and cation donor
preference. Dalton Transactions 2003, 7, 1264−1271.
(68) Miller, K. J.; Saherwala, A. A.; Webber, B. C.; Wu, Y.; Sherry, A.
D.; Woods, M. The population of SAP and TSAP isomers in cyclen-
based lanthanide (III) chelates is substantially affected by solvent.
Inorg. Chem. 2010, 49 (19), 8662−8664.
(69) Aime, S.; Botta, M.; Garda, Z.; Kucera, B. E.; Tircso, G.; Young,
V. G.; Woods, M. Properties, Solution State Behavior, and Crystal
Structures of Chelates of DOTMA. Inorg. Chem. 2011, 50 (17),
7955−7965.
(70) Mayer, F.; Platas-Iglesias, C.; Helm, L.; Peters, J. A.;
Djanashvili, K. 17O NMR and Density Functional Theory Study of
the Dynamics of the Carboxylate Groups in DOTA Complexes of
Lanthanides in Aqueous Solution. Inorg. Chem. 2012, 51 (1), 170−
178.
(84) Tripier, R.; Platas-Iglesias, C.; Boos, A.; Morfin, J. F.;
̀
Charbonniere, L. Towards Fluoride Sensing with Positively Charged
Lanthanide Complexes. Eur. J. Inorg. Chem. 2010, 2010 (18), 2735−
2745.
(85) Liu, T.; Nonat, A.; Beyler, M.; Regueiro-Figueroa, M.; Nchimi
́
Nono, K.; Jeannin, O.; Camerel, F.; Debaene, F.; Cianferani-Sanglier,
̀
S.; Tripier, R.; Platas-Iglesias, C.; Charbonniere, L. J. Supramolecular
Luminescent Lanthanide Dimers for Fluoride Sequestering and
Sensing. Angew. Chem., Int. Ed. 2014, 53 (28), 7259−7263.
(86) Blackburn, O. A.; Chilton, N. F.; Keller, K.; Tait, C. E.; Myers,
W. K.; McInnes, E. J. L.; Kenwright, A. M.; Beer, P. D.; Timmel, C.
R.; Faulkner, S. Spectroscopic and Crystal Field Consequences of
Fluoride Binding by [Yb-DTMA]3+ in Aqueous Solution. Angew.
Chem., Int. Ed. 2015, 54 (37), 10783−10786.
(87) Blackburn, O. A.; Kenwright, A. M.; Beer, P. D.; Faulkner, S.
Axial fluoride binding by lanthanide DTMA complexes alters the local
crystal field, resulting in dramatic spectroscopic changes. Dalton
Transactions 2015, 44 (45), 19509−19517.
́
(71) Desreux, J. F.; Barthelemy, P. P. Highly stable lanthanide
macrocyclic complexes: in search of new contrast agents for NMR
imaging. International Journal of Radiation Applications and Instru-
mentation. Part B. Nuclear Medicine and Biology 1988, 15 (1), 9−15.
(72) Gale, E. M.; Caravan, P.; Rao, A. G.; McDonald, R. J.; Winfeld,
M.; Fleck, R. J.; Gee, M. S. Gadolinium-based contrast agents in
(88) Mason, K.; Harnden, A. C.; Patrick, C. W.; Poh, A. W. J.;
Batsanov, A. S.; Suturina, E. A.; Vonci, M.; McInnes, E. J. L.; Chilton,
N. F.; Parker, D. Exquisite sensitivity of the ligand field to solvation
and donor polarisability in coordinatively saturated lanthanide
K
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