Understanding the Quenching Effects of Aromatic C-H- and C-D-Oscillators in Near-IR Lanthanoid Luminescence

被引:97
作者
Doffek, Christine [2 ]
Alzakhem, Nicola [2 ]
Bischof, Caroline [2 ]
Wahsner, Jessica [2 ]
Gueden-Silber, Tuba [2 ]
Luegger, Joachim [2 ]
Patas-Iglesias, Carlos [1 ]
Seitz, Michael [2 ]
机构
[1] Univ A Coruna, Dept Quim Fundamental, La Coruna 15008, Spain
[2] Ruhr Univ Bochum, Dept Chem & Biochem, D-44780 Bochum, Germany
关键词
ENERGY-GAP LAW; LANTHANIDE(III) COMPLEXES; INDUCED SHIFTS; LOCAL MODES; RELAXATION; DECAY; IONS; INTENSITIES; MOLECULES; RESONANCE;
D O I
10.1021/ja307339f
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Several series of selectively deuterated 2,2'-bipyridine-based cryptates with the near-IR emissive lanthanoids Pr, Nd, Er, and Yb are reported. The structural and luminescence properties of these complexes have been comprehensively investigated. A combination of experimental techniques (X-ray crystallography, lanthanoid-induced NMR shift analysis, luminescence, vibrational near-IR absorption) and theoretical concepts has been applied with a focus on nonradiative deactivation through multiphonon relaxation of lanthanoid excited states by aromatic, high-energy C-(H/D) oscillators. It is shown that the characteristics for the overtones of these vibrational modes deviate substantially from harmonic oscillators and that anharmonicity within a local-mode Morse model is an essential parameter for any accurate description. The spectral overlap integrals (SOIs) of lanthanoid electronic states with aromatic C-(H/D) overtones are evaluated quantitatively for different lanthanoid/oscillator combinations and the implications for luminescence enhancement through deuteration is discussed. Simple Gaussian functions are proposed as appropriate mathematical forms for the empirical approximation of SOIs.
引用
收藏
页码:16413 / 16423
页数:11
相关论文
共 41 条
[1]   DETERMINATION OF METAL PROTON DISTANCES AND ELECTRONIC RELAXATION-TIMES IN LANTHANIDE COMPLEXES BY NUCLEAR-MAGNETIC-RESONANCE SPECTROSCOPY [J].
AIME, S ;
BARBERO, L ;
BOTTA, M ;
ERMONDI, G .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (02) :225-228
[2]  
Basiev TT, 1997, LASER PHYS, V7, P1139
[3]   Non-radiative deactivation of the excited states of europium, terbium and ytterbium complexes by proximate energy-matched OH, NH and CH oscillators: an improved luminescence method for establishing solution hydration states [J].
Beeby, A ;
Clarkson, IM ;
Dickins, RS ;
Faulkner, S ;
Parker, D ;
Royle, L ;
de Sousa, AS ;
Williams, JAG ;
Woods, M .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1999, (03) :493-503
[4]  
Beeby A., 2002, DALTON T, P1923
[5]   VIBRATIONAL ANALYSIS OF C-H STRETCHING OVERTONES IN PYRIDINE AND 2,6-LUTIDINE [J].
BINI, R ;
FOGGI, P ;
DELLAVALLE, RG .
JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (08) :3027-3031
[6]   Quantification of C-H Quenching in Near-IR Luminescent Ytterbium and Neodymium Cryptates [J].
Bischof, Caroline ;
Wahsner, Jessica ;
Scholten, Julia ;
Trosien, Simon ;
Seitz, Michael .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (41) :14334-14335
[7]   Lanthanide NIR luminescence for telecommunications, bioanalyses and solar energy conversion [J].
Buenzli, Jean-Claude G. ;
Eliseeva, Svetlana V. .
JOURNAL OF RARE EARTHS, 2010, 28 (06) :824-842
[8]   APPLICATION OF THE ENERGY-GAP LAW TO THE DECAY OF CHARGE-TRANSFER EXCITED-STATES [J].
CASPAR, JV ;
KOBER, EM ;
SULLIVAN, BP ;
MEYER, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (02) :630-632
[9]  
Casper J.V., 1983, INORG CHEM, V105, P2444
[10]   OVERTONE FREQUENCIES AND INTENSITIES IN THE LOCAL MODE PICTURE [J].
CHILD, MS ;
HALONEN, L .
ADVANCES IN CHEMICAL PHYSICS, 1984, 57 :1-58