Striking solvent dependence of total emission and circularly polarised luminescence in coordinatively saturated chiral europium complexes: solvation significantly perturbs the ligand field

被引：13

作者：

Fradgley, Jack D. ^{[1
]}

Frawley, Andrew T. ^{[1
]}

Pal, Robert ^{[1
]}

Parker, David ^{[1
]}

机构：

[1] Univ Durham, Dept Chem, South Rd, Durham DH1 3LE, England

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2021年 / 23卷 / 19期

基金：

英国工程与自然科学研究理事会;

关键词：

LANTHANIDE COMPLEXES; CRYSTAL SPECTRA; SENSITIZATION; STEREOCONTROL; TRANSITIONS; INTENSITIES; INVERSION; EU(III); BRIGHT; SHIFTS;

D O I：

10.1039/d1cp01686e

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Examination of total emission and circularly polarised luminescence (CPL) spectra of three 9-coordinate Eu(iii) complexes with well-defined speciation shows that the ligand fields of these C-3 symmetric complexes are extremely sensitive to solvent polarity, even when solvent is not present in the first coordination sphere. The energies, intensities, and (for CPL) the sign of some transitions vary with solvent polarity. These observations are rationalised by analysis of the factors that control total and circularly polarised emission, and have important implications for design of responsive luminescent Ln(iii) probes.

引用

页码：11479 / 11487

页数：9

共 44 条

[1] Interpretation of europium(III) spectra [J].

Binnemans, Koen .

COORDINATION CHEMISTRY REVIEWS, 2015, 295 :1-45

[2] Design, synthesis and evaluation of ratiometric probes for hydrogencarbonate based on europium emission [J].

Bretonniere, Y ;

Cann, MJ ;

Parker, D ;

Slater, R .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2004, 2 (11) :1624-1632

[3] Utility of tris(4-bromopyridyl) europium complexes as versatile intermediates in the divergent synthesis of emissive chiral probes [J].

Butler, Stephen J. ;

Delbianco, Martina ;

Evans, Nicholas H. ;

Frawley, Andrew T. ;

Pal, Robert ;

Parker, David ;

Puckrin, Robert S. ;

Yufit, Dmitry S. .

DALTON TRANSACTIONS, 2014, 43 (15) :5721-5730

[4] Efficient Sensitization of Europlum, Ytterbium, and Neodymium Functionalized Tris-Dipicolinate Lanthanide Complexes through Tunable Charge-Transfer Excited States [J].

D'Aleo, Anthony ;

Picot, Alexandre ;

Beeby, Andrew ;

Williams, J. A. Gareth ;

Le Guennic, Boris ;

Andraud, Chantal ;

Maury, Olivier .

INORGANIC CHEMISTRY, 2008, 47 (22) :10258-10268

[5] New Class of Bright and Highly Stable Chiral Cyclen Europium Complexes for Circularly Polarized Luminescence Applications [J].

Dai, Lixiong ;

Lo, Wai-Sum ;

Coates, Ian D. ;

Pal, Robert ;

Law, Ga-Lai .

INORGANIC CHEMISTRY, 2016, 55 (17) :9065-9070

[6] Solution structure of chiral lanthanide complexes [J].

Di Bari, L ;

Salvadori, P .

COORDINATION CHEMISTRY REVIEWS, 2005, 249 (24) :2854-2879

[7] 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 [J].

Dickins, RS ;

Parker, D ;

Bruce, JI ;

Tozer, DJ .

DALTON TRANSACTIONS, 2003, (07) :1264-1271

[8] Complete stereocontrol in the synthesis of macrocyclic lanthanide complexes: direct formation of enantiopure systems for circularly polarised luminescence applications [J].

Evans, Nicholas H. ;

Carr, Rachel ;

Delbianco, Martina ;

Pal, Robert ;

Yufit, Dmitry S. ;

Parker, David .

DALTON TRANSACTIONS, 2013, 42 (44) :15610-15616

[9] Enantioselective cellular localisation of europium(III) coordination complexes [J].

Frawley, Andrew T. ;

Linford, Holly V. ;

Starck, Matthieu ;

Pal, Robert ;

Parker, David .

CHEMICAL SCIENCE, 2018, 9 (04) :1042-1049

[10] Very bright, enantiopure europium(III) complexes allow time-gated chiral contrast imaging [J].

Frawley, Andrew T. ;

Pal, Robert ;

Parker, David .

CHEMICAL COMMUNICATIONS, 2016, 52 (91) :13349-13352

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