A photoinduced mixed valence photoswitch

被引：9
作者：
Cotic, Agustina [1 ,2 ]
Cerfontaine, Simon [3 ]
Slep, Leonardo D. [1 ,2 ]
Elias, Benjamin [3 ]
Troian-Gautier, Ludovic [3 ]
Cadranel, Alejandro [1 ,2 ,4 ,5 ]
机构：
[1] Univ Buenos Aires, Fac Ciencias Exactas & Nat, Dept Quim Inorgan Analit & Quim Fis, Pabellon 2,Ciudad Univ,C1428EHA, Buenos Aires, DF, Argentina
[2] Univ Buenos Aires, Inst Quim Fis Mat Medio Ambiente & Energia INQUIM, CONICET, Pabellon 2,Ciudad Univ,C1428EHA, Buenos Aires, DF, Argentina
[3] Univ Catholique Louvain UCLouvain, Inst Matiere Condensee & Nanosci IMCN, Mol Chem Mat & Catalysis MOST, Pl Louis Pasteur 1,Bte L4-01-02, B-1348 Louvain La Neuve, Belgium
[4] Friedrich Alexander Univ Erlangen Nurnberg FAU, Phys Chem 1, Egerlandstr 3, D-91058 Erlangen, Germany
[5] Friedrich Alexander Univ Erlangen Nurnberg FAU, Interdisciplinary Ctr Mol Mat, Egerlandstr 3, D-91058 Erlangen, Germany
来源：
PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2022年 / 24卷 / 24期
关键词：
TRANSIENT ABSORPTION-SPECTROSCOPY; STATE INTERVALENCE TRANSFER; ELECTRON-TRANSFER; POLYPYRIDINE COMPLEXES; CORRESPONDING ORBITALS; RUTHENIUM(II); TRINUCLEAR; SYSTEMS; 2,2'-BIPYRIDINE; 4,4'-BIPYRIDINE;
D O I：
10.1039/d2cp01791a
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：
The ground state and photoinduced mixed valence states (GSMV and PIMV, respectively) of a dinuclear (Dp(4+)) ruthenium(ii) complex bearing 2,2 '-bipyridine ancillary ligands and a 2,2 ':4 ',4 '':2 '',2 '''-quaterpyridine (Lp) bridging ligand were investigated using femtosecond and nanosecond transient absorption spectroscopy, electrochemistry and density functional theory. It was shown that the electronic coupling between the transiently light-generated Ru(ii) and Ru(iii) centers is H-DA similar to 450 cm(-1) in the PIMV state, whereas the electrochemically generated GSMV state showed H-DA similar to 0 cm(-1), despite virtually identical Ru-Ru distances. This stemmed from the changes in dihedral angles between the two bpy moieties of Lp, estimated at 30 degrees and 4 degrees for the GSMV and PIMV states, respectively, consistent with a through-bond rather than a through-space mechanism. Electronic coupling can be turned on by using visible light excitation, making Dp(4+) a competitive candidate for photoswitching applications. A novel strategy to design photoinduced charge transfer molecular switches is proposed.
引用
收藏
页码：15121 / 15128
页数：8
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