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The Dark Side of Hydrogen Bonds in the Design of Optical Materials: A Charge‐Density Perspective
Author(s) -
Nelyubina Yulia V.,
Puntus Lada N.,
Lyssenko Konstantin A.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201300566
Subject(s) - lanthanide , hydrogen bond , redistribution (election) , molecule , coordination sphere , excited state , charge (physics) , chemistry , luminescence , chemical physics , photochemistry , ion , ground state , hydrogen , crystallography , outer sphere electron transfer , atomic physics , materials science , organic chemistry , physics , optoelectronics , quantum mechanics , politics , political science , law
A combined investigation of the structural, electronic, and optical properties of three crystalline nonaaqualanthanoid(III) triflates, [Ln(H 2 O) 9 (CF 3 SO 3 ) 3 ], has provided unambiguous experimental evidence for charge redistribution in the first coordination sphere of a lanthanide ion as a result of hydrogen bonds with outer‐sphere anions. As well as resulting in charge transfer from the noncoordinated anions to the coordinated water molecules, these hydrogen bonds give rise to a new excited state, an hydrogen‐bond‐induced charge‐transfer state, which is observed experimentally for the first time. This state was shown to be responsible for the previously unknown negative aspect of hydrogen bonds with a lanthanide‐bound water molecule: rather than increasing the luminescence efficiency of the complex, they can lead to additional quenching that is unfavorable for the task‐specific design of optical materials.